Controlled Architecture Polymers

ABSTRACT

Acrylic copolymers that include the controlled placement of particular functional groups within the polymer structure are provided. The copolymers contain at least two reactive segments and are manufactured via a controlled radical polymerization process. The copolymers are useful in the manufacture of adhesives and elastomers.

CROSS REFERENCES TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 14/351,686 filed Apr. 14, 2014, which is a 371 of InternationalApplication No. PCT/US2012/059849. International Application No.PCT/US2012/059849 was published in English on Apr. 18, 2013, and claimsthe benefit of U.S. Provisional Patent Application No. 61/547,481 filedOct. 14, 2011, all of which are incorporated herein by reference intheir entireties.

BACKGROUND

The subject matter relates to acrylic polymers, and in particular, toacrylic copolymers that include controlled placement of reactivefunctional groups within the polymer structure. The copolymers areuseful in the manufacture of adhesives and elastomers.

(Meth)acrylic (co)polymers have been studied and used industrially formore than 50 years. Due to a wide range of monomers, (meth)acrylic(co)polymers display a significant array of viscoelastic properties thatlend themselves well to applications in adhesives and elastomers. Whencompared to other copolymers that are used for similar purposes as(meth)acrylics, several significant advantages of (meth)acrylics becomeapparent. For example, relative to natural rubber and styrene blockcopolymers (meth)acrylic copolymers have superior optical clarity, UVstability, and temperature and oxidative resistance. State of the art(meth)acrylic copolymers meet many performance characteristics by virtueof their high molecular weight and crosslinking reactions. Because ofthe wide array of copolymerizable monomers, (meth)acrylic polymers havetailorable polarity and the ability to undergo a variety of crosslinkingreactions. Typically high performance (meth)acrylic copolymers areprocessed with large amounts of organic solvents.

Increasingly, there are significant economic and regulatory pressuresfor producers of solvent acrylic polymers to reduce the use of organicsolvents in their processes. In particular, it is common for solventacrylic polymers in adhesive applications to be coated from solutionsaveraging only 30-40% polymer. The solvent has to be evaporated and theneither collected or incinerated, all of which are energy intensive andcostly operations. Additionally, removal of solvent from thick adhesivefilms may produce defects in the dry adhesive film.

Control of polymer architecture is often the subject of intensiveresearch with the goal of improving performance for ever increasinglychallenging applications. Architectures that acrylic polymers are knownto possess include block copolymers, telechelic polymers, and randompolymers of controlled molecular weight. Even though advances incontrolling architecture have occurred with many benefits, each of theseparticular architectural types has disadvantages. For example, blockcopolymers have high melt viscosities which require high processingtemperatures, making it difficult to control reactivity of functionalgroups. The production of telechelic polymers often involves multiplesteps. Telechelics involve the placement of a reactive functional groupexclusively on the end terminus of a polymer and not elsewhere in thepolymer backbone. Functional groups placed at the end termini ofpolymers serve solely to increase the linear molecular weight in amanner in which free polymer chain ends are eliminated. As a result,telechelic polymers can yield high strength materials but do not providethe viscoelastic properties critical to adhesives and some elastomerapplications. Random polymers of controlled molecular weight requirehigh amounts of crosslinking to attain network formation.

In the past 15-20 years a variety of controlled radical polymerizationtechniques have been developed to afford good architectural control of(meth)acrylic monomers. These techniques typically are tolerant to awide variety of monomers and functional groups as opposed to previoustechniques like anionic or group transfer polymerization. A substantialamount of fundamental research has been performed to understand thesetypes of polymerization and a thorough review has been edited byMatyjewski. Reversible addition fragmentation chain transfer (RAFT)polymerization is one such technique that has been shown to workexceedingly well with a wide variety of (meth)acrylic monomers yieldingexcellent control of molecular weight and polydispersity. The RAFTmechanism for controlled polymerization is well understood and reportedextensively. While some examples of controlled architecture acrylic PSAshave been reported, very little work has been done to explore theinfluence of reactive functional group placement.

SUMMARY

The present subject matter addresses problems associated with previouslyknown architectured polymers by placement of crosslinkable monomers intosegments of the polymer of controlled molecular weight and position. Theoverall molecular weight is low which yields desirable low viscosity,high solids solutions and melts. In conjunction with goodprocessability, high performance elastomers and adhesives are obtainedupon crosslinking. In particular, the crosslinkable monomers are placedin specific segments of the polymer backbone so that the crosslinkdensity is controlled for optimal performance. The compositions of thepresent subject matter contain no undesired heterogeneity prior tocrosslinking. A further benefit is that in all embodiments of thesubject matter, the polymer chain ends are preserved to yield desiredvisco-elastic and surface properties. To control the placement ofcrosslinkable monomers, it is preferred to employ a controlled freeradical polymerization technique. In contrast with standard free radicalprocesses it is now possible to control the placement of crosslinkablemonomers.

In one aspect, the present subject matter provides an acrylic polymercomprising a first reactive segment that includes at least one monomerhaving a self reactive functional group. The acrylic polymer alsocomprises a second reactive segment that includes at least one monomerhaving a reactive functional group.

In another aspect, the present subject matter provides a crosslinkablecomposition comprising an acrylic polymer including a first reactivesegment that includes at least one monomer having a self reactivefunctional group, and a second reactive segment that includes at leastone monomer having a reactive functional group.

In yet another aspect, the present subject matter provides a method ofpreparing a crosslinkable composition comprising polymerizing at leastone monomer having a self reactive functional group to thereby form afirst reactive segment. The method also comprises polymerizing at leastone monomer having a reactive functional group to thereby form a secondreactive segment. At least one of the first reactive segment and thesecond reactive segment includes an acrylate group. The method alsocomprises forming an acrylic polymer from the first reactive segment andthe second reactive segment.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graph of viscosity as a function of solids content for highglass transition temperature polymeric samples described herein.

FIG. 2 is a graph of viscosity as a function of solids content for lowglass transition temperature polymeric samples described herein.

DETAILED DESCRIPTION

Acrylic copolymers prepared by sequential polymerization of polymersegments from various monomers are provided. The preferred embodimentcopolymers contain a first reactive segment preferably at a polymerchain end and at least one other or a second reactive segment preferablyat another polymer chain end. The first reactive segment includes atleast one functional group that is capable of undergoing a crosslinkingreaction. Preferably, the second reactive segment also includes at leastone functional group that is capable of undergoing a crosslinkingreaction. The reactive segments have controlled size and placement fortailored properties. For example, by selectively placing functionalgroups in desirable positions on a polymer molecule, polymers that yieldpressure sensitive adhesives that exhibit enhanced balance betweencohesion and adhesion can be produced. In certain embodiments thepolymers also include a third segment which is located between the firstreactive segment and the second reactive segment. The third segmentpreferably includes at least one reactive functionality and/or anonreactive segment. Also provided are adhesive compositions based uponthe various polymers, and methods of preparing the polymers.

High modulus elastomers and high strength adhesives typically display aconstant modulus as a function of temperature. Conversely, highlyextensible, tough elastomers, and high tack and peel adhesives oftenhave a degree of viscous liquid character. One route to this behavior isthrough control of crosslink density via placement of reactivefunctionalities in specific segments of the polymer. Placing reactivefunctionalities in segments adjacent to the polymer end groups yieldshigh modulus and high strength. Placing the reactive functionalities inthe central segment(s) of the polymer yields significant viscous liquidcharacter. As described herein, the present subject matter providesstrategies for controlling the structure and architecture of polymersand thereby enabling production of compositions having specific anddesired characteristics.

Polymers and Crosslinkable Compositions

Generally, the present subject matter provides an acrylic polymer havinga first reactive segment that includes at least one monomer having aself reactive functional group, and a second reactive segment thatincludes at least one monomer having a reactive functional group. Thereactive functionalities in the first reactive segment and the secondreactive segment may be the same or different from one another. A widearray of reactive functionalities can be included in the first andsecond reactive segments. In certain embodiments, the reactivefunctional group of the second reactive segment is a self reactivefunctional group as in the first reactive segment. The self reactivefunctional group in the second reactive segment may be the same ordifferent than the self reactive functional group of the first reactivesegment. And, in certain embodiments, the second reactive segment isfree of a self reactive functional group.

The term “reactive functional group” refers to a functional group thatis capable of reacting with another functional group. The term “selfreactive functional group” refers to a functional group that is capableof reacting with (i) an identical second self reactive functional group,(ii) with a different second self reactive functional group and/or (iii)with a reactive functional group. That is, the self reactive functionalgroup can react with another identical self reactive functional group,with another self reactive functional group that is different, and/orwith a reactive functional group. Self reactive functional groups arecapable of polymerizing with themselves. Preferably, the self reactivefunctional group is selected from anhydrides, epoxies, alkoxymethylols,and cyclic ethers. Non-limiting examples of reactive functional groupsare provided herein, however preferably include acids, hydroxyls,amines, and mercapto (thiols).

In another embodiment of the subject matter, there is provided acrosslinkable composition comprising at least one acrylic copolymerhaving a first reactive segment of controlled size and position and atleast one other or second reactive segment of controlled size andposition. The first reactive segment comprises at least one monomerhaving a self reactive functional group as described herein. The otheror second reactive segment comprises at least one monomer having areactive functional group and is preferably reactive with the selfreactive functional group of the first reactive segment. The secondreactive segment may contain a group that is capable of undergoingcrosslinking while remaining reactive with the reactive segment. Theacrylic copolymer of the crosslinkable composition may in certainembodiments also preferably comprise a third polymeric segment. Thethird polymeric segment preferably includes a reactive functionalityand/or a nonreactive segment. Additional aspects as described inconjunction with the previously described preferred embodiment acryliccopolymers are included in the examples described herein.

In certain embodiments, the acrylic copolymers preferably include atleast one nonreactive segment. The nonreactive segments of the acrylicpolymer may be derived from acrylates, methacrylates, or mixturesthereof. The acrylates include C₁ to about C₂₀ alkyl, aryl or cyclicacrylates such as methyl acrylate, ethyl acrylate, phenyl acrylate,butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, n-heptylacrylate, n-octyl acrylate, n-nonyl acrylate, isobornyl acrylate,2-propyl heptyl acrylate, isodecyl acrylate, isostearyl acrylate and thelike. These moieties typically contain from about 3 to about 20 carbonatoms, and in one embodiment about 3 to about 8 carbon atoms. Themethacrylates include C₁ to about C₂₀ alkyl, aryl or cyclicmethacrylates such as methyl methacrylate, ethyl methacrylate, butylmethacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, isobornylmethacrylate, isooctyl methacrylate, and the like. These moietiestypically contain from about 4 to about 20 carbon atoms, and in oneembodiment about 3 to about 10 carbon atoms.

The preferred embodiment polymers exhibit relatively narrow ranges ofmolecular weight and thus have relatively low polydispersity values.Typically, the preferred embodiment polymers exhibit polydispersity(Pdi) values of less than 4.0, preferably less than 3.5, more preferablyless than 3.0, more preferably less than 2.5, and most preferably lessthan 2.0. In certain embodiments, the preferred embodiment polymersexhibit polydispersities of less than 1.5, and as low as about 1.4. Thepreferred embodiment polymers typically have a number average molecularweight (Mn) of from about 40,000 to about 150,000, and preferably about50,000 to about 110,000. However, it will be appreciated that thesubject matter includes polymers having molecular weights and/orpolydispersity values greater than or less than the values noted herein.

Reactive Segments

The reactive segments of the acrylic polymer may be a copolymer derivedfrom one or more of the monomers of a nonreactive segment and at leastone polymerizable comonomer having crosslinkable functionality. In oneembodiment, the reactive segment comprises at least one monomer havingthe formula (I):

where R is H or CH₃ and X represents or contains a functional groupcapable of crosslinking. The crosslinkable functional group of thereactive segment of the acrylic polymer is not particularly restricted,but may include one or more crosslinkable silyl, hydroxyl, carboxyl,carbonyl, carbonate ester, isocyanate, epoxy, vinyl, amine, amide,imide, anhydride, mercapto (thiol), acid, acrylamide, acetoacetylgroups, alkoxymethylol, and cyclic ether groups. As previously noted,the functional group of at least one reactive segment is a self reactivefunctional group and most preferably is selected from the previouslynoted collection of self reactive functional groups.

Hydroxy functional monomers include, for example, hydroxy ethyl(meth)acrylate, hydroxy isopropyl (meth)acylate, hydroxy butyl(meth)acrylate and the like.

Epoxy functional monomers include, for example, glycidyl methacrylateand glycidal acrylate. In certain embodiments, a particularly preferredepoxy functional monomer is commercially available under the designationS-100 from Synasia. That monomer is 3, 4 epoxycydohexylmethylmethacrylate, [CAS 82428-30-6], having a chemical formula C₁₁H₁₆O₃ and amolecular weight of 196.2.

The acid containing monomers include, for example, unsaturatedcarboxylic acids containing from 3 to about 20 carbon atoms. Theunsaturated carboxylic acids include, among others, acrylic acid,methacrylic acid, itaconic acid, beta carboxy ethyl acrylate,mono-2-acroyloxypropyl succinate, and the like. It is contemplated thatphosphoric acids may be used.

Anhydride containing monomers include, for example, maleic anhydride,itaconic anhydride, citraconic anhydride and the like.

The acrylamides include, for example, acrylamide and its derivativesincluding the N-substituted alkyl and aryl derivatives thereof. Theseinclude N-methyl acrylamide, N,N-dimethyl acrylamide, t-octyl acrylamideand the like. The methacrylamides include methacrylamide and itsderivatives including the N-substituted alkyl and aryl derivativesthereof.

Vinyl groups include, for example, vinyl esters, vinyl ethers, vinylamides, and vinyl ketones. The vinyl esters include vinyl acetate, vinylpropionate, vinyl butyrate, vinyl valerate, vinyl versitate, vinylisobutyrate and the like. The vinyl ethers include vinyl ethers having 1to about 8 carbon atoms including ethylvinyl ether, butylvinyl ether,2-ethylhexylvinyl ether and the like. The vinyl amides include vinylamides having 1 to about 8 carbon atoms including vinyl pyrrolidone, andthe like. The vinyl ketones include vinyl ketones having 1 to about 8carbon atoms including ethylvinyl ketone, butylvinyl ketone, and thelike.

Silyl groups include, for example, polymerizable silanes. Thepolymerizable silanes include vinyltrimethoxysilane,vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane,vinylmethyldiethoxy-silane, vinylmethyldipropoxysilane,γ-methacryloxypropyl-trimethoxysilane,γ-methacryloxypropyltriethoxysilane,γ-methacryloxypropyl-tripropoxysilane, γ-methacryloxydimethoxysilane,γ-methacryloxypropyl-methyldimethoxysilane,γ-methacryloxypropylmethyldiethoxysilane,γ-methacryl-oxypropylmethyldipropoxysilane,γ-methacryloxymethyl-dimethoxysilane,γ-methacryloxymethyltrimethoxysilane,γ-methacryloxymethyl-triethoxy-silane, (methacryloxymethyl)methyldimethoxysilane, (methacryloxymethyl)-methyldiethoxysilane,γ-methacryloxypropyltriacetoxysilane, γ-acryloxypropyltrimethoxy-silane,γ-acryloxypropyltriethoxy-silane, γ-methacryl-oxymethyldiethoxysilane,γ-acryloxypropyltripropoxy-silane,γ-acryloxypropyl-methyldimethoxysilane,γ-acryloxypropylmethyldiethoxysilane,γ-acryloxypropyl-methyldipropoxysilane, and the like.

In addition to the monomer having functional group(s), the reactivesegment may include at least one monomer having the formula (II):

where R₃ is H or CH₃ and R₄ is a branched or unbranched, saturated alkylgroup having 4 to 14 carbon atoms.

Methods

The present subject matter also provides, in another embodiment, amultiple step polymerization process for making a crosslinkable acryliccopolymer having a first reactive segment with one or more self reactivefunctional groups provided by at least one monomer. Preferably, themonomer is an acrylic monomer. A second reactive segment is added to thefirst segment to form the acrylic copolymer. The second reactive segmentpreferably contains one or more crosslinkable functional groups and ismiscible with the first segment. As used herein, the term “molecularlymiscible” means a compound or mixture of compounds that exhibitproperties in the bulk state that are indicative of single phasebehavior. With respect to the acrylic copolymer, the observation of asingle Tg is indicative of polymer segment miscibility. The single Tg isintermediate between those of the constituent polymer segments andvaries monotonically between these values as the relative amounts ofeach segment changes.

In an alternative embodiment, there is provided a process for making acrosslinkable acrylic copolymer having a first segment including selfreactive functional groups, and a second segment having reactivefunctional groups provided by at least one monomer, which is preferablyan acrylic monomer. The second segment is reacted with the first segmentto form the acrylic copolymer.

With conventional free-radical polymerization, polymers are terminatedwhen the reactive free radical end group is destroyed via termination orchain transfer reactions. The termination and chain transfer processesare typically irreversible and yield a polymer that is inactive. Theresult of this is a broad molecular weight distribution and littlecontrol over the distribution of monomers in the polymer backbone.Controlled radical polymerizations involve reversible radical processesin which irreversible termination and chain transfer are largely absent.There are three main types of controlled radical polymerizationmethodologies including atom transfer radical polymerization (ATRP),reversible addition-fragmentation chain transfer (RAFT), and stable freeradical polymerization (SFRP) (of which nitroxide mediatedpolymerization (NMP) is a subset). RAFT and SFRP are particularly usefulmethods because of their tolerance to a wide array of functional groupsand their efficiency and versatility in producing controlled radicalpolymerized polymers.

The acrylic copolymers of the subject matter are prepared using any ofthe controlled radical polymerization processes, which includeatom-transfer radical polymerization (ATRP); rapidaddition-fragmentation chain transfer (RAFT); and stable free radicalpolymerization (SFRP). Nitroxide-mediated polymerization (NMP) is anexample of an SFRP process.

ATRP involves the chain initiation of free radical polymerization by ahalogenated organic species in the presence of a metal halide species.The metal has a number of different oxidation states that allows it toabstract a halide from the organohalide, creating a radical that thenstarts free radical polymerization. After initiation and propagation,the radical on the chain active chain terminus is reversibly terminated(with the halide) by reacting with the catalyst in its higher oxidationstate. A simplified mechanism for reversible activation-deactivation ofpolymer chains during ATRP is shown in Scheme 1. Thus the redox processgives rise to an equilibrium between dormant (polymer-halide) and active(polymer-radical) chains. The equilibrium is designed to heavily favorthe dormant state, which effectively reduces the radical concentrationto sufficiently low levels to limit bimolecular coupling.

The initiator in ATRP is usually a low molecular weight activatedorganic halide (RX, R=activated alkyl, X=chlorine, bromine, iodine).However, organic pseudohalides (e.g., X=thiocyanate, azide) andcompounds with weak N—X (e.g., N-bromosuccinimide) or S—X (e.g.,sulfonyl halides) may be used. ATRP can be mediated by a variety ofmetals, including Ti, Mo, Re, Fe, Ru, Os, Rh, Co, Ni, Pd and Cu.Complexes of Cu offer the most efficient catalysts in the ATRP of abroad range of monomer in diverse media. Commonly used nitrogen-basedligands used in conjunction with Cu ATRP catalysts include derivativesof bidentate bipyridine and pyridine imine, tridentatediethylenetriamine and tetradentate tris[2-aminoethylene]amine andtetraazacyclotetradecane.

Controlled polymerization by RAFT occurs via rapid chain transferbetween growing polymer radicals and dormant polymer chains. Afterinitiation, the control agent becomes part of the dormant polymer chain.The key mechanistic features of RAFT are illustrated in Scheme 2. CommonRAFT agents contain thiocarbonyl-thio groups, and include, for example,dithioesters, dithiocarbamates, trithiocarbonates and xanthenes.Examples of useful RAFT agents include those described in “The Chemistryof Radical Polymerization”, Graeme Moad & David H. Solomon, 2^(nd) rev.ed., 2006, Elsevier, p. 508-514, which is incorporated by referenceherein.

Initiation and radical-radical termination occur as in conventionalradical polymerization. In the early stages of the polymerization,addition of a propagating radical (Pn^(•)) to the thiocarbonylthiocompound followed by fragmentation of the intermediate radical givesrise to a polymeric thiocarbonylthio compound and a new radical (R^(•)).Reaction of the radical (R^(•)) with monomer forms a new propagatingradical (Pm^(•)). A rapid equilibrium between the active propagatingradicals (Pn^(•) and Pm^(•)) and the dormant polymeric thiocarbonylthiocompounds provides equal probability for all chains to grow and allowsfor the production of narrow dispersity polymers.

SFRP, and in particular, NMP achieves control with dynamic equilibriumbetween dormant alkoxyamines and actively propagating radicals. The useof nitroxides to mediate (i.e., control) free radical polymerization hasbeen developed extensively. Many different types of nitroxides have beendescribed and there are many methods for producing nitroxides in-situ.Regardless of the nitroxide or its method of generation, the keymechanistic feature of NMP is reversible coupling of the nitroxide(i.e., R2NO) to a growing polymer chain radical (P^(•)) as shown inScheme 3.

Examples of useful NMP agents include those described in “The Chemistryof Radical Polymerization”, Graeme Moad & David H. Solomon, 2^(nd) rev.ed., 2006, Elsevier, p. 473-475, which is incorporated by referenceherein. An example of a commercially available NMP agent isBlocBuilder®, an alkoxyamine compound that acts an initiator and controlagent, available from Arkema.

The methods for forming the preferred embodiment acrylic polymerspreferably use one or more polymerization catalysts. The polymerizationcatalyst can be, for example, organic tin compounds, metal complexes,amine compounds and other basic compounds, organic phosphate compounds,and organic acids. Examples of the organic tin compounds includedibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, stannousoctoate, dibutyltin methoxide, dibutyltin diacetylacetate and dibutyltindiversatate. Examples of metal complexes are titanate compounds such astetrabutyl titanate, tetraisopropyl titanate, and tetraethanolaminetitanate; metal salts of carboxylic acids, such as lead octoate, leadnaphthoate, and cobalt naphthoate; and metal acetylacetonate complexessuch as aluminum acetylacetonate complex and vanadium acetylacetonatecomplex. The amine compounds and other basic compounds include, forexample aminisilanes such as γ-aminopropyl trimethoxysilane andγ-aminopropyltriethoxysilane; quaternary ammonium salts such astetramethylammonium chloride and benzalkonium chloride; andstraight-chain or cyclic tertiary amines or quaternary ammonium saltseach containing plural nitrogen atoms. The organic phosphate compoundsinclude monomethyl phosphate, di-n-butyl phosphate and triphenylphosphate. Examples of organic acid catalysts include alkyl sulfonicacids such as methane sulfonic acid, aryl sulfonic acids such asp-toluene sulfonic acid, benzene sulfonic acid, styrene sulfonic acidand the like.

Adhesives

Adhesives having a wide array of properties can be formed from theacrylic polymers and/or compositions described herein. Generally, theacrylic polymers described herein are crosslinked and combined with oneor more components to provide an adhesive composition. The preferredembodiment adhesives are preferably pressure sensitive adhesives. Thepolymer may be crosslinked during post curing of the adhesive toincrease the cohesive strength of the pressure sensitive adhesive. Thiscan be achieved via covalent crosslinking such as heat, actinic orelectron beam radiation, or metal based ionic crosslinking betweenfunctional groups. Table 1 below lists representative examples ofcrosslinkers for various functional groups of the segmented polymer.

TABLE 1 Crosslinkers Functional Group of Segmented Polymer CrosslinkerSilane (Silyl) Self-reactive Hydroxyl Isocyanate, Melamine Formaldehyde,Anhydride, Epoxy, Titanium esters and Chelates Carboxylic acid,Aziridines, Isocyanate, Melamine Formaldehyde, phosphoric acidAnhydride, Epoxy, Carboiimides, Metal Chelates, Titanium esters andOxazolines Isocyanate Self-reactive, Carboxylic acid, Amine, HydroxylVinyl Addition reaction with Silicone hydride (Meth)acrylate Amine,Mercaptan, Self-reactive with radical catalyst (UV, Thermal),Acetoacetate Epoxy Amine, Carboxylic acid, Phosphoric acid, Hydroxyl,Mercaptan Amine Isocyanate, Melamine formaldehyde, anhydride, epoxy,acetoacetate Mercapto (thiol) Isocyanate, Melamine formaldehyde,Anhydride, Epoxy Acetoacetate Acrylate, Amine Alkoxymethylol Acid,Hydroxyl, Thiol (Mercapto), Amine Cylic Ethers Hydroxyl, Amines, Thiol(Mercapto)

Suitable polyfunctional aziridines include, for example,trimethylolpropane tris[3-aziridinylpropionate]; trimethylolpropanetris[3-(2-methylaziridinyl) propionate]; trimethylolpropanetris[2-aziridinylbutyrate]; tris(1-aziridinyl)-phosphine oxide;tris(2-methyl-1-aziridinyl)phosphine oxide;penta-erythritoltris[3-(1-aziridinyl)propionate]; and pentaerythritoltetrakis[3-(1-aziridinyl)propionate]. Combinations of more than onepolyfunctional aziridine may also be used. Examples of commerciallyavailable polyfunctional aziridines include NEOCRYL CX-100 from ZenecaResins, believed to be trimethylolpropatentris[3-(2-methylaziridinyl)-propanoate], and Xama-2, Xama-7 and Xama-220from Bayer Material Science.

Multifunctional aziridine amides which have the general formula (III):

wherein R can be either an alkylene or aromatic group and R′ can be ahydrogen or alkyl group and x is at least 2 may be used. Examples ofsuitable multifunctional aziridine amides include1,1′-(1,3-phenylenedicarbonyl)bis[2-methyl aziridine];2,2,4-trimethyladipoyl bis [2-ethyl aziridine]; 1,1′-azelaoyl bis[2-methyl aziridine]; and 2,4,6-tris(2-ethyl-l-aziridinyl)-1,3,5triazine.

Metal chelate crosslinking agents may be compounds prepared bycoordinating multivalent metals such as Al, Fe, Zn, Sn, Ti, Sb, Mg and Vwith acethylacetone or ethyl acetoacetonate.

Among the isocyanate crosslinking agents that can be used are aromatic,aliphatic and cycloaliphatic diisocyanates and triisocyanates. Examplesinclude 2,4-toluene diisocyanate, m-phenylene diisocyanate,4-chloro-1,3-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylenediisocyanate, 4,4′-diphenylene diisocyanate, xylene diisocyanate,1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate,1,4-cyclohexylene diisocyanate, 4,4′methylene bis(cyclohexylisocyanate), 1,5-tetrahydronaphthalene diisocyanate, paraxylylenediisocyanate, durene diisocyante, 1,2,4-benzene diisocyanate, isoformdiisocyanate, 1,4-tetramethylxylene diisocyanate, 1,5-naphthalenediisocyanate, or their reactants with polyol such as trimethylolpropane.

Other useful crosslinking agents include monomeric and polymericmelamine crosslinkers, such as Cymel 303 and 370 available from Cytec.

The crosslinking agent is typically used at a level from about 0.05% toabout 5%, or from about 0.075% to about 2%, or from about 0.1% to about1.5% by weight of adhesive solids.

Anhydride functional segmented polymers may be converted to silanes viaa post polymerization reaction with amino-, mercapto- orhydroxyl-functional silanes. Examples of amino group-containingalkoxysilanes having a primary amino group alone as a reactive groupinclude aminoalkyltrialkoxysilanes such as aminomethyltrimethoxysilane,aminomethyltriethoxysilane, β-amino-ethyltrimethoxysilane,β-aminoethyltriethoxysilane, γ-aminopropyltrimeth-oxysilane,γ-aminopropyltriethoxysilane, γ-aminopropyltripropoxysilane,γ-aminopropyltriisopropoxysilane, and γ-aminopropyltributoxysilane;(aminoalkyl)-alkyldialkoxysilanes such asβ-aminoethylmethyldimethoxysilane, γ-amino-ethylmethyldiethoxysilane,γ-aminopropylmethyldimethoxysilane, γ-aminopropyl-methyldiethoxysilane,and γ-aminopropylmethyldipropoxysilane; and correspondingaminoalkyldialkyl(mono)alkoxysilanes.

Examples of amino group-containing alkoxysilanes having a primary aminogroup and a secondary amino group as reactive groups includeN-(aminoalkyl)aminoalkyltrialkoxysilanes such asN-β-(aminoethyl)-γ-aminopropyl-trimethoxysilane andN-β-(aminoethyl)-γ-aminopropyltriethoxysilane; andN-(aminoalkyl)aminoalkylalkyldialkoxysilanes such asN-β-(aminoethyl)-γ-amino-propylmethyldimethoxysilane andN-β-(aminoethyl)-γ-aminopropylmethyl-diethoxysilane.

Examples of amino group-containing alkoxysilanes having a secondaryamino group alone as a reactive group includeN-phenylamino-methyltrimethoxysilane andN-phenyl-β-aminoethyltrialkoxysilanes such asN-phenyl-β-aminoethyltrimethoxysilane andN-phenyl-β-aminoethyltriethoxysilane;N-phenyl-γ-aminopropyltrialkoxysilanes such asN-phenyl-γ-aminopropyltrimethoxysilane,N-phenyl-γ-aminopropyltriethoxysilane,N-phenyl-γ-aminopropyltripropoxysilane, andN-phenyl-γ-aminopropyltributoxysilane; correspondingN-phenylaminoalkyl(mono- or di-)alkyl(di- or mono-)alkoxysilanes; aswell as N-alkylaminoalkyltrialkoxysilanes corresponding to theabove-listed amino group-containing alkoxysilanes having a secondaryamino group substituted with phenyl group, such asN-methyl-3-aminopropyltrimethoxysilane,N-ethyl-3-aminopropyltrimethoxysilane,N-n-propyl-3-aminopropyltrimethoxysilane,N-n-butyl-aminomethyltrimethoxysilane,N-n-butyl-2-aminoethyltrimethoxysilane,N-n-butyl-3-aminopropyltrimethoxysilane,N-n-butyl-3-aminopropyltriethoxysilane, andN-n-butyl-3-aminopropyltripropoxysilane, and correspondingN-alkylaminoalkyl(mono- or di-)alkyl(di- or mono)alkoxysilanes. Othersinclude N-cyclohexylaminomethylmethyldiethoxy silane andN-cyclohexylaminomethyl-triethoxysilane.

Examples of the mercapto group-containing silanes includemercaptoalkyltrialkoxysilanes such as mercaptomethyltrimethoxysilane,mercaptomethyltriethoxysilane, β-mercaptoethyltrimethoxysilane,β-mercapto-ethyltriethoxysilane, β-mercaptoethyltripropoxysilane,β-mercaptoethyl-triisopropoxysilane, β-mercaptoethyltributoxysilane,γ-mercaptopropyl-trimethoxysilane, γ-mercaptopropyltriethoxysilane,γ-mercaptopropyltri-propoxysilane, γ-mercaptopropyltriisopropoxysilane,and γ-mercapto-propyltributoxysilane;(mercaptoalkyl)alkyldialkoxysilanes such asβ-mercaptoethylmethyldimethoxysilane,β-mercaptoethylmethyldiethoxysilane,γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane,γ-mercaptopropylmethyldipropoxysilane,β-mercaptopropylmethyldiisopropoxy-silane,γ-mercaptopropylmethyldibutoxysilane,β-mercaptopropylmethyldibutoxysilane,γ-mercaptopropylethyldimethoxy-silane,γ-mercaptopropylethyldiethoxysilane,γ-mercaptopropylethyldipropoxy-silane,γ-mercaptopropylethyldiisopropoxysilane, andγ-mercaptopropyl-ethyldibutoxysilane; and corresponding(mercaptoalkyl)dialkyl(mono)-alkoxysilanes.

Examples of hydroxyl-functional silanes include hydroxymethyltrialkoxysilanes having the formula (IV):

Where R is an alkyl group and n is at least 1. The alkyl group ispreferably a lower alkyl group having 1 to 6 carbon atoms, andpreferably 1 to 3 carbon atoms. Particularly useful are the silanes inwhich the alkyl group is methyl or ethyl, namelyhydroxymethyltriethoxysilane and hydroxymethyltriethoxysilane when n isequal to 1.

The adhesives of the present subject matter may further compriseadditives such as pigments, fillers, plasticizer, diluents,antioxidants, tackifiers and the like. Pigment, if desired, is providedin an amount sufficient to impart the desired color to the adhesive.Examples of pigments include, without limitation, solid inorganicfillers such as carbon black, titanium dioxide and the like, and organicdyes. Additional inorganic fillers such as aluminum trihydrate,christobalite, glass fibers, kaolin, precipitated or fumed silica,copper, quartz, wollasonite, mica, magnesium hydroxide, silicates (e.g.feldspar), talc, nickel and calcium carbonate are also useful. Metaloxides such as aluminum trihydrate and magnesium hydroxide areparticularly useful as flame retardants.

A wide variety of tackifiers can be used to enhance the tack and peel ofthe adhesive. These include rosins and rosin derivatives includingrosinous materials that occur naturally in the oleoresin of pine trees,as well as derivatives thereof including rosin esters, modified rosinssuch as fractionated, hydrogenated, dehydrogenated, and polymerizedrosins, modified rosin esters and the like.

There may also be employed terpene resins which are hydrocarbons of theformula C₁₀H₁₆, occurring in most essential oils and oleoresins ofplants, and phenol modified terpene resins like alpha pinene, betapinene, dipentene, limonene, myrecene, bornylene, camphene, and thelike. Various aliphatic hydrocarbon resins like Escorez 1304,manufactured by Exxon Chemical Co., and aromatic hydrocarbon resinsbased on C₉, C₅, dicyclopentadiene, coumarone, indene, styrene,substituted styrenes and styrene derivatives and the like can also beused.

Hydrogenated and partially hydrogenated resins such as Regalrez 1018,Regalrez 1033, Regalrez 1078, Regalrez 1094, Regalrez 1126, Regalrez3102, Regalrez 6108, etc., produced by Eastman Chemical Company, can beused. Various terpene phenolic resins of the type SP 560 and SP 553,manufactured and sold by Schenectady Chemical Inc., Nirez 1100,manufactured and sold by Reichold Chemical Inc., and Piccolyte S-100,manufactured and sold by Hercules Corporation, are particularly usefultackifiers for the present subject matter. Various mixed aliphatic andaromatic resins, such as Hercotex AD 1100, manufactured and sold byHercules Corporation, can be used.

While the resins described above are quite useful for tackifying thecopolymers of the instant subject matter, the particular tackifyingresin and/or amount selected for a given formulation may depend upon thetype of acrylic polymer being tackified. Many resins which are known inthe prior art as being useful for tackifying acrylic based pressuresensitive adhesives can be effectively used in the practice of thepresent subject matter, although the scope of the subject matter is notlimited to only such resins. Resins described in Satas, Handbook ofPressure Sensitive Adhesive Technology, Von Nostrand Reinhold, Co, Chap.20, pages 527-584 (1989) (incorporated by reference herein) could beused.

The amount of tackifier used in the present subject matter is dependentupon the type of copolymer and tackifier used. Typically, pressuresensitive adhesive compositions prepared in accordance with the presentsubject matter will comprise from 5 to about 60% by weight total of oneor more tackifiers.

In one embodiment, the tackifier has a ring and ball softening point offrom about 100° C. to about 150° C. In one embodiment, the tackifiercomprises a terpene phenolic tackifier having a ring and ball softeningpoint of from about 110° C. to about 120° C.

In another embodiment, the added resin may serve a dual purpose. Forexample, a resin such as Wingstay L®, a butylated reaction product ofpara-cresol and dicyclopentadiene with an average molecular weight of650 produced by Eliokem, can serve both as a tackifier and anantioxidant.

In one embodiment, a low molecular weight polymeric additive isincorporated into the adhesive composition. The polymeric additive ispolymerized from monomers selected from C₁-C₂₀ alkyl and cycloalkylacrylates, C₁-C₂₀ alkyl and cycloalkyl methacrylates, free radicalpolymerizable olefinic acids, and optionally other ethylenicallyunsaturated monomers. Suitable alkyl and cycloalkyl acrylates includethe various esters of acrylic acid such as methyl acrylate, ethylacrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,isobutyl acrylate, t-butyl acrylate, isobornyl acrylate, pentylacrylate, hexyl acrylate, octyl acrylate, iso-octyl acrylate, nonylacrylate, lauryl acrylate, stearyl acrylate, eicosyl acrylate,2-ethylhexyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate, andthe like and mixtures thereof. Suitable alkyl and cycloalkylmethacrylate include the esters of methacrylic acid such as methylmethacrylate, ethyl methacrylate, propyl methacrylate, n-butylmethacrylate, t-butyl methacrylate, isobutyl methacrylate, pentylmethacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexylmethacrylate, isobornyl methacrylate, heptyl methacrylate, cycloheptylmethacrylate, octyl methacrylate, iso-octyl methacrylate, nonylmethacrylate, decyl methacrylate, lauryl methacrylate, eicosylmethacrylate and the like and mixtures thereof. Suitable free-radicalpolymerizable olefinic acids include acrylic acid, methacrylic acid,fumaric acid, crotonic acid, itaconic acid, 2-acryloxypropionic acid,and the like and mixtures thereof.

Various amounts of other ethylenically-unsaturated monomers canoptionally be used provided that the polymeric additive has a softeningpoint greater than about 40° C. and a number average molecular weightless than about 35,000. Optional ethylenically-unsaturated monomerssuitable for use in the polymeric additive include, for example,styrene, alpha-methyl styrene, vinyl toluene, acrylonitrile,methacrylonitrile, ethylene, vinyl acetate, vinyl chloride, vinylidenechloride, acrylamide, methacrylamide 2-cyanoethyl acrylate, 2-cyanoethylmethacrylate, dimethylaminoethyl methacrylate, dimethylaminopropylmethacrylate t-butylaminoethyl methacrylate, glycidyl acrylate, glycidylmethacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate,phenyl methacrylate and the like. The amount of the polymeric additiveused may be in the range of about 1% to about 55% by weight, based onthe total weight of the adhesive composition. Such low molecular weightadditives as described in U.S. Pat. No. 4,912,169, the disclosure ofwhich is hereby incorporated by reference.

Certain preferred embodiment adhesives have a relatively high solidscontent. Typically, the weight percentage of solids is greater than 50%,more preferably at least 60%, and more preferably at least 70%.

FIG. 1 is a graph of viscosity as a function of solids content forseveral preferred embodiment polymers described herein. Specifically,these “high acid” polymers are prepared and evaluated as described ingreater detail herein. FIG. 2 is a similar graph of viscosity as afunction of solids content for two preferred embodiment polymersdescribed herein. Specifically, these “low acid” polymers are preparedand evaluated in greater detail herein.

Examples

The following test methods were used for evaluating the adhesiveproperties of the acrylic adhesives.

Various 180° peel tests were used in evaluating preferred embodimentpressure sensitive adhesives prepared from preferred embodiment acrylicpolymers. Also performed were shear strength tests and shear adhesionfailure temperature tests (SAFT). These tests were performed assummarized in Table 2.

TABLE 2 Pressure Sensitive Adhesive Performance Test Methods TestCondition 180° Peel a, b 15 Minute Dwell 24 Hour Dwell 72 Hour DwellShear Strength c Shear Adhesion Failure Temp. (SAFT) d a Peel, sampleapplied to a stainless steel panel with a 5 pound roller with 1 pass ineach direction. Samples conditioned and tested at 23° C. b Peel, sampleapplied to a high density polyethylene (HDPE) or polypropylene (PP) witha 5 pound roller with 5 passes in each direction. Samples conditionedand tested at 23° C. c Shear: 1 kg weight with a ½ inch by 1 inchoverlap. Sample applied to a stainless steel panel with a 10 poundroller with 5 passes in each direction. Samples conditioned and testedat 23° C. d SAFT: 1000 gram weight, 1 inch by 1 inch overlap (2.2pounds/square inch). Sample applied to a stainless steel panel with a 10pound roller with 5 passes in each direction. Samples conditioned for 1hour at 23° C. and 15 minutes at 40° C. Temperature increased by 0.5°C./min. until failure.

The subject matter is further described by reference to the followingnon-limiting examples.

Example 1: Epoxy Hybrid Functional Acrylic Polymer

An acrylic copolymer with reactive functionalities positioned in thesegment adjacent to the polymer chain ends is prepared as follows. Intoa 1500 ml vessel equipped with a heating jacket, agitator, refluxcondenser, feed tanks and nitrogen gas inlet there is charged 65.06 g ofethyl acetate and 10.50 g of methanol. Monomers and RAFT agent are addedin the following amounts to generate the segment adjacent to the polymerchain ends:

36.53 g butyl acrylate

41.57 g of 2 ethyl-hexyl acrylate

4.87 g of dibenzyl trithiocarbonate (RAFT agent 50% solution in ethylacetate)

6.58 g of 3,4 epoxycyclohexyl methyl methacrylate (cyclo aliphaticepoxy)

0.275 g of VAZO® 64 (AIBN)

After a 30 minute reactor sparge with nitrogen at room temperature, thereactor charge is heated to reflux conditions (reactor jacket 95° C.)with a constant nitrogen purge. After a peak temperature of 75-78° C. isattained, the reaction conditions are maintained for 30 minutes at whichpoint >70% of the monomers are consumed. A reagent feed mixture with anactive nitrogen purge of 230.38 g ethyl acetate, 31.49 g of methanol,374.13 g 2-ethyl-hexyl acrylate, 328.78 g butyl acrylate, 58.79 g ofacrylic acid, and 0.28 g VAZO® 64 is added over a period of two and onehalf hours to the reactor. VAZO® 64 is a free radical source,commercially available from DuPont. Over the reagent feed thetemperature of the reaction under reflux is held under 85° C. Thereaction conditions are maintained for 3 hours after completion of thereagent feed at which point >97.0% of the monomers are consumed. Theresulting solution polymer is then cooled to ambient and discharged fromthe reactor.

The resulting acrylic polymer contains 43.2% butyl acrylate, 49.1%2-ethyl-hexyl acrylate, 7% acrylic acid and 0.70% 3,4 epoxycyclohexylmethyl methacrylate based on 100% by weight of the acrylic polymer. Themeasured molecular weight (Mn) of the acrylic polymer is 51,991(determined by gel permeation chromatography relative to polystyrenestandards) and the polydispersity is 2.12.

0.4% based on solids aluminum acetyl acetonate (AAA) was added to theacrylic polymer. The adhesive composition is air dried for 5 minutesthen placed into an air forced oven at 120° C. for 10 minutes.

The adhesives are coated onto 2-mil polyethylene terephthalate at 58-62grams per square meter (gsm) and air dried for 5 minutes followed by a10 minute 120° C. dry.

Example 2: Epoxy Hybrid Functional Acrylic Polymer

An acrylic copolymer with reactive functionalities positioned in thesegment adjacent to the polymer chain ends is prepared as follows. Intoa 1500 ml vessel equipped with a heating jacket, agitator, refluxcondenser, feed tanks and nitrogen gas inlet there is charged 65.26 g ofethyl acetate and 10.53 g of methanol. Monomers and RAFT agent are addedin the following amounts to generate the segment adjacent to the polymerchain ends:

37.05 g butyl acrylate

42.11 g of 2-ethyl-hexyl acrylate

4.88 g of dibenzyl trithiocarbonate (RAFT agent 50% solution in ethylacetate)

3.30 g of 3,4 epoxycyclohexyl methyl methacrylate (cyclo aliphaticepoxy)

0.276 g of VAZO® 64 (AIBN)

After a 30 minute reactor sparge with nitrogen at room temperature, thereactor charge is heated to reflux conditions (reactor jacket 95° C.)with a constant nitrogen purge. After a peak temperature of 75-78° C. isattained, the reaction conditions are maintained for 30 minutes at whichpoint >70% of the monomers are consumed. A reagent feed mixture with anactive nitrogen purge of 135.79 g ethyl acetate, 31.58 g of methanol,378.95 g 2-ethyl-hexyl acrylate, 333.47 g butyl acrylate, 50.53 g ofacrylic acid, and 0.28 g Vazo-64 is added over a period of two and onehalf hours to the reactor. Over the reagent feed the temperature of thereaction under reflux is held under 85° C. The reaction conditions aremaintained for 3 hours after completion of the reagent feed at whichpoint >97.0% of the monomers are consumed. The resulting solutionpolymer is then cooled to ambient and discharged from the reactor.

The resulting acrylic polymer contains 43.8% butyl acrylate, 49.8%2-ethyl-hexyl acrylate, 6% acrylic acid and 0.40% 3,4 epoxycyclohexylmethyl methacrylate based on 100% by weight of the acrylic polymer. Themeasured molecular weight (Mn) of the acrylic polymer is 62,898(determined by gel permeation chromatography relative to polystyrenestandards) and the polydispersity is 1.53.

0.7% based on solids aluminum acetyl acetonate was added to the acrylicpolymer. The adhesive composition is air dried for 5 minutes then placedinto an air forced oven at 120° C. for 10 minutes.

The adhesives are coated onto 2-mil polyethylene terephthalate at 58-62grams per square meter (gsm) and air dried for 5 minutes followed by a10 minute 120° C. dry.

Example 3: Epoxy Hybrid Functional Acrylic Polymer

An acrylic copolymer with reactive functionalities positioned in thesegment adjacent to the polymer chain ends is prepared as follows. Intoa 1500 ml vessel equipped with a heating jacket, agitator, refluxcondenser, feed tanks and nitrogen gas inlet there is charged 59.02 g ofethyl acetate and 9.52 g of methanol. Monomers and RAFT agent are addedin the following amounts to generate the segment adjacent to the polymerchain ends:

34.27 g butyl acrylate

38.84 g of 2-ethyl-hexyl acrylate

2.94 g of dibenzyl trithiocarbonate (RAFT agent 50% solution in ethylacetate)

1.99 g of 3,4 epoxycyclohexyl methyl methacrylate (cyclo aliphaticepoxy)

0.083 g of VAZO® 64 (AIBN)

After a 30 minute reactor sparge with nitrogen at room temperature, thereactor charge is heated to reflux conditions (reactor jacket 95° C.)with a constant nitrogen purge. After a peak temperature of 75-78° C. isattained, the reaction conditions are maintained for 30 minutes at whichpoint >70% of the monomers are consumed. A reagent feed mixture with anactive nitrogen purge of 230.38 g ethyl acetate, 28.5 g of methanol,349.57 g 2-ethyl-hexyl acrylate, 308.45 g butyl acrylate, 30.46 g ofacrylic acid, and 0.08 g VAZO® 64 is added over a period of two and onehalf hours to the reactor. Over the reagent feed the temperature of thereaction under reflux is held under 85° C. The reaction conditions aremaintained for 3 hours after completion of the reagent feed at whichpoint >97.0% of the monomers are consumed. The resulting solutionpolymer is then cooled to ambient and discharged from the reactor.

The resulting acrylic polymer contains 44.9% butyl acrylate, 50.8%2-ethyl-hexyl acrylate, 4% acrylic acid and 0.3% 3,4 epoxycyclohexylmethyl methacrylate based on 100% by weight of the acrylic polymer. Themeasured molecular weight (Mn) of the acrylic polymer is 60,369(determined by gel permeation chromatography relative to polystyrenestandards) and the polydispersity is 1.79.

0.6% based on solids aluminum acetyl acetonate (AAA) was added to theacrylic polymer. The adhesive composition is air dried for 5 minutesthen placed into an air forced oven at 120° C. for 10 minutes.

The adhesives are coated onto 2-mil polyethylene terephthalate at 58-62grams per square meter (gsm) and air dried for 5 minutes followed by a10 minute 120° C. dry.

Example 4: Preparation of Segmented Acrylic Polymer Having EpoxyFunctionality in the Endblocks and Acid Functionality Throughout UsingRAFT Agent

An acrylic copolymer with segmented acrylic polymer having epoxyfunctionality in the endblocks and acid functionality throughout isprepared as follows. Into a 1500 ml reactor equipped with a heatingjacket, agitator, reflux condenser, feed tanks and nitrogen gas inletthe following is charged:

142.50 g of butyl acetate

105.37 g of ethyl acetate

15.00 g of methanol

3.92 g of Synasia S-100 epoxy monomer

54.00 g of 2-ethylhexyl acrylate

36.61 g of methyl acrylate

9.00 g of acrylic acid

2.90 g of dibenzyl trithiocarbonate (DBTTC)

02.87 g of VAZO® 88 (polymerization initiator from DuPont)

Into a 1000 ml feed vessel fitted with nitrogen gas inlet, monomers andsolvents are added in the following amounts to generate a portion ofonly acid functional reactive segment at the center of the polymer chainends of the epoxy/acid reactive polymer mode:

105.20 g of ethyl acetate

34.87 g of methanol

486.00 g of 2-ethylhexyl acrylate

329.47 g of methyl acrylate

81.00 g of acrylic acid

The reactor charge is heated to 80° C. (reactor jacket 95° C.) with aconstant nitrogen purge and held for 30 minutes. After the hold, thereagent feed mixture with an active nitrogen purge is added over aperiod of 182 minutes to the reactor. During the reagent feed thetemperature of the reaction is held between 80-85° C. The reactionconditions are maintained after completion of the reagent feed for 90minutes. This is to create the remainder of the only acid reactivesegment at the center of the polymer, the total theoretical Mn of theacid reactive segment is 90,000 g/mol. At this time, 0.87 g of t-amylperoxy pivalate and 87.50 g of toluene are added and reaction conditionsare maintained for 45 minutes. The resulting solution polymer is thencooled to ambient temperature and discharged from the reactor.

The resulting epoxy/acid reactive acrylic polymer contains 54.00%2-ethylhexyl acrylate, 36.61% methyl acrylate, 9.00% acrylic acid, and0.39% Synasia S-100 based on 100% by weight of the reactive acrylicpolymer. The resulting acid only reactive polymer mode contains 54.00%2-ethylhexyl acrylate, 37.00% methyl acrylate, and 9.00% acrylic acid.The measured molecular weight (Mn) of the total acrylic polymer is57,197 g/Mole (determined by gel permeation chromatography relative topolystyrene standards) and the polydispersity is 1.89.

Aluminum acetoacetonate in an amount of 0.60% based on solids was addedto the acrylic polymer. The adhesive composition is dried at 120° C. for10 minutes to ensure complete crosslinking of the acrylic polymer.

Example 5: Preparation of Segmented Acrylic Polymer Having EpoxyFunctionality in the Endblocks and Acid Functionality Throughout UsingRAFT Agent

An acrylic copolymer with segmented acrylic polymer having epoxyfunctionality in the endblocks and acid functionality throughout isprepared as follows. Into a 1500 ml reactor equipped with a heatingjacket, agitator, reflux condenser, feed tanks and nitrogen gas inletthe following is charged:

142.50 g of butyl acetate

105.37 g of ethyl acetate

15.00 g of methanol

3.92 g of Synasia S-100 epoxy monomer

55.00 g of 2-ethylhexyl acrylate

37.61 g of methyl acrylate

7.00 g of acrylic acid

2.90 g of dibenzyl trithiocarbonate (DBTTC)

2.87 g of VAZO® 88

Into a 1000 ml feed vessel fitted with nitrogen gas inlet, monomers andsolvents are added in the following amounts to generate a portion ofonly acid functional reactive segment at the center of the polymer chainends of the epoxy/acid reactive polymer mode:

105.20 g of ethyl acetate

34.87 g of methanol

495.00 g of 2-ethylhexyl acrylate

338.47 g of methyl acrylate

63.00 g of acrylic acid

The reactor charge is heated to 80° C. (reactor jacket 95° C.) with aconstant nitrogen purge and held for 30 minutes. After the hold, thereagent feed mixture with an active nitrogen purge is added over aperiod of 182 minutes to the reactor. During the reagent feed thetemperature of the reaction is held between 80-85° C. The reactionconditions are maintained after completion of the reagent feed for 90minutes. This is to create the remainder of the only acid reactivesegment at the center of the polymer, the total theoretical Mn of theacid reactive segment is 90,000 g/mol. At this time, 0.87 g of t-amylperoxy pivalate and 87.50 g of toluene are added and reaction conditionsare maintained for 45 minutes. The resulting solution polymer is thencooled to ambient temperature and discharged from the reactor.

The resulting epoxy/acid reactive acrylic polymer mode contains 55.00%2-ethylhexyl acrylate, 37.61% methyl acrylate, 7.00% acrylic acid, and0.39% Synasia S-100 based on 100% by weight of the reactive acrylicpolymer mode. The resulting acid only reactive polymer mode contains55.00% 2-ethylhexyl acrylate, 38.00% methyl acrylate, and 7.00% acrylicacid. The measured molecular weight (Mn) of the total acrylic polymer is60,592 g/Mole (determined by gel permeation chromatography relative topolystyrene standards) and the polydispersity is 1.90.

Aluminum acetoacetonate in an amount of 0.60% based on solids was addedto the acrylic polymer. The adhesive composition is dried at 120° C. for10 minutes to ensure complete crosslinking of the acrylic polymer.

Example 6: Preparation of Segmented Acrylic Polymer Having EpoxyFunctionality in the Endblocks and Acid Functionality Throughout UsingRAFT Agent

An acrylic copolymer with segmented acrylic polymer having epoxyfunctionality in the endblocks and acid functionality throughout isprepared as follows. Into a 1500 ml reactor equipped with a heatingjacket, agitator, reflux condenser, feed tanks and nitrogen gas inletthe following is charged.

131.18 g of butyl acetate

97.00 g of ethyl acetate

13.81 g of methanol

2.41 g of Synasia S-100 epoxy monomer

49.71 g of 2-ethylhexyl acrylate

33.82 g of methyl acrylate

8.29 g of acrylic acid

1.78 g of dibenzyl trithiocarbonate (DBTTC)

1.76 g of VAZO® 88

Into a 1000 ml feed vessel fitted with nitrogen gas inlet, monomers andsolvents are added in the following amounts to generate a portion ofonly acid functional reactive segment at the center of the polymer chainends of the epoxy/acid reactive polymer mode:

131.18 g of ethyl acetate

32.11 g of methanol

447.40 g of 2-ethylhexyl acrylate

304.38 g of methyl acrylate

74.57 g of acrylic acid

The reactor charge is heated to 80° C. (reactor jacket 95° C.) with aconstant nitrogen purge and held for 60 minutes. After the hold, thereagent feed mixture with an active nitrogen purge is added over aperiod of 176 minutes to the reactor. During the reagent feed thetemperature of the reaction is held between 80-85° C. The reactionconditions are maintained after completion of the reagent feed for 90minutes. This is to create the remainder of the only acid reactivesegment at the center of the polymer, the total theoretical Mn of theonly acid reactive segment is 135,000 g/mol. At this time, 0.81 g oft-amyl peroxy pivalate and 80.55 g of butyl acetate are added andreaction conditions are maintained for 45 minutes. The resultingsolution polymer is then cooled to ambient temperature, diluted with87.46 g of butyl acetate and discharged from the reactor.

The resulting epoxy/acid reactive acrylic polymer mode contains 54.00%2-ethylhexyl acrylate, 36.74% methyl acrylate, 9.00% acrylic acid, and0.26% Synasia S-100 based on 100% by weight of the reactive acrylicpolymer mode. The resulting acid only reactive polymer mode contains54.00% 2-ethylhexyl acrylate, 37.00% methyl acrylate, and 9.00% acrylicacid. The measured molecular weight (Mn) of the total acrylic polymer is63,887 g/mole (determined by gel permeation chromatography relative topolystyrene standards) and the polydispersity is 2.11.

Aluminum acetoacetonate in an amount of 0.60% based on solids was addedto the acrylic polymer. The adhesive composition is dried at 120° C. for10 minutes to ensure complete crosslinking of the acrylic polymer.

Example 7: Preparation of Segmented Acrylic Polymer Having EpoxyFunctionality in the Endblocks and Acid Functionality Throughout UsingRAFT Agent

An acrylic copolymer with segmented acrylic polymer having epoxyfunctionality in the endblocks and acid functionality throughout isprepared as follows. Into a 1500 ml reactor equipped with a heatingjacket, agitator, reflux condenser, feed tanks and nitrogen gas inletthe following is charged:

131.18 g of butyl acetate

92.40 g of ethyl acetate

13.81 g of methanol

2.41 g of Synasia S-100 epoxy monomer

50.63 g of 2-ethylhexyl acrylate

34.74 g of methyl acrylate

6.44 g of acrylic acid

1.78 g of dibenzyl trithiocarbonate (DBTTC)

1.76 g of VAZO® 88

Into a 1000 ml feed vessel fitted with nitrogen gas inlet, monomers andsolvents are added in the following amounts to generate a portion ofonly acid functional reactive segment at the center of the polymer chainends of the epoxy/acid reactive polymer mode.

131.18 g of ethyl acetate

32.11 g of methanol

455.69 g of 2-ethylhexyl acrylate

312.67 g of methyl acrylate

58.00 g of acrylic acid

The reactor charge is heated to 80° C. (reactor jacket 95° C.) with aconstant nitrogen purge and held for 60 minutes. After the hold, thereagent feed mixture with an active nitrogen purge is added over aperiod of 176 minutes to the reactor. During the reagent feed thetemperature of the reaction is held between 80-85° C. The reactionconditions are maintained after completion of the reagent feed for 90minutes. This is to create the remainder of the only acid reactivesegment at the center of the polymer, the total theoretical Mn of theonly acid reactive segment is 135,000 g/mol. At this time, 0.81 g oft-amyl peroxy pivalate and 80.55 g of butyl acetate are added andreaction conditions are maintained for 45 minutes. The resultingsolution polymer is then cooled to ambient temperature, diluted with87.46 g of butyl acetate and discharged from the reactor.

The resulting epoxy/acid reactive acrylic polymer mode contains 55.00%2-ethylhexyl acrylate, 37.74% methyl acrylate, 7.00% acrylic acid, and0.26% Synasia S-100 based on 100% by weight of the reactive acrylicpolymer mode. The resulting acid only reactive polymer mode contains55.00% 2-ethylhexyl acrylate, 38.00% methyl acrylate, and 7.00% acrylicacid. The measured molecular weight (Mn) of the total acrylic polymer is76,119 g/mole (determined by gel permeation chromatography relative topolystyrene standards) and the polydispersity is 2.07.

Aluminum acetoacetonate in an amount of 0.60% based on solids was addedto the acrylic polymer. The adhesive composition is dried at 120° C. for10 minutes to ensure complete crosslinking of the acrylic polymer.

The adhesives were coated onto 2-mil aluminum foil at 58-62 grams persquare meter (gsm) and dried at 120° C. for 10 minutes.

Adhesives of Examples 1-7

Table 3 set forth below summarizes wet physical properties of adhesivesprepared using the polymers of Examples 1-7 and two commerciallyavailable adhesives. Table 4 summarizes pressure sensitive adhesiveproperties of adhesives prepared using the polymers of Examples 1-7 andtwo commercially available adhesives. The first commercial adhesivedesignated as “Commercial Adhesive 1” in Tables 3 and 4 iscompositionally comparable to the preferred embodiment adhesives ofExamples 1-3. And, the second commercial adhesive designated as“Commercial Adhesive 2” in Tables 3 and 4 is compositionally comparableto the preferred embodiment adhesives of Examples 4-7. Referring toTable 3, it will be noted that the preferred embodiment adhesives ofExamples 1-7 exhibit a significantly narrower range of molecular weightsand polydispersity values, for example Pdi values range from 1.41 to2.11 as compared to the molecular weight ranges and polydispersityvalues of the two commercially available adhesives, i.e. Pdi values of6.2 and 6.75. In addition, the preferred embodiment adhesives ofExamples 1-7 exhibit a significantly higher solids content (i.e. 62% to73%) as compared to that of the two commercially available adhesives(i.e. 36% to 50%).

Referring to Table 4, it is evident that the PSA performance of thepreferred embodiment adhesives of Examples 1-7 are comparable to and incertain instances, significantly superior to those of the twocommercially available adhesives.

TABLE 3 Wet Physical Properties of Adhesives of Polymers of Examples 1-7Sample Acid Molecular Weight % Viscosity Name Monomers Level T_(g) (degC.) Targeted Mn Mw Pdi Solids (cps) Example 1 EHA/BA 7 −60 100 Example2EHA/BA 6 −60 100 62898 96248 1.53 72 10640 Example 3 EHA/BA 4 −60 10060506 85370 1.41 73 8300 Commercial EHA/BA 4 −60 NA 57000 350000 6.2 504000 Adhesive 1 Example 4 EHA/MA 9 −35 100 57197 107980 1.89 71 45400Example 5 EHA/MA 7 −35 100 60592 115500 1.91 72 31160 Example 6 EHA/MA 9−35 150 63887 134520 2.11 62 32080 Example 7 EHA/MA 7 −35 150 76119157670 2.07 63 28800 Commercial EHA/MA 7 −35 NA 105000 709000 6.75 3613000 Adhesive 2

TABLE 4 Properties of Adhesives of Polymers of Examples 1-7 180° Peel180° Peel 180° Peel 180° Peel 180° Sample SS 15 min SS 24 hr SS 72 hrHDPE 72 hr Peel PP 8.8 lbs/in² Name (pli) (pli) (pli) (pli) 72 hr (pli)Shear (min) SAFT (° C.) Example 1 5.15 m 5.55 m 5.71 m 0.38 a 3.05 a 1904 m >200 Example 2 3.01 a 7.03 c 9.06 c 0.44 a 2.56 a   199 m >200Example 3 2.66 a 5.47 m 6.78 m 0.4 a 2.72 a   92.0 a >200 Commercial5.64 m 7.05 c 7.85 c 0.55 a 2.56 a   52.0 c  90 c Adhesive 1 Example 44.39 a 5.39 a 6.18 a NA NA >10000 >200 Example 5 3.48 a 5.21 a 6.03 a NANA >10000 >200 Example 6 4.12 a 5.64 a 6.04 a NA NA >10000 >200 Example7 4.04 a 4.79 a 5.48 a NA NA >10000 >200 Commercial 4.07 a 5.25 a 5.70 aNA NA >10000 >200 Adhesive 2

Examples 8-23: Analysis and Investigation of Polymers with High and LowGlass Transition Temperatures Example 8

Various samples of polymers having high glass transition temperatures(Tg), e.g., about −35° C., and low glass transition temperatures, e.g.,about −60° C., were prepared. Two different molecular weights weretargeted: 100,000 (or “100” as noted below) and 150,000 (or “150”).Hybrid epoxy functional polymers were formed from loadings of 4%, 6%,7%, and 9% on monomers of acrylic acid. Tables 3-5 summarize thesepolymers. In the sample name designations, L is for low Tg, H is forhigh Tg, 4 is for 4% acid, 6 is for 6% acid, 7 is for 7% acid, 9 is for9% acid, 150 is for 150K molecular weight, and 100 is for 100K molecularweight.

TABLE 5 Summary of Examples and Sample Properties Sample Name PreparedAccording to L6.100 Example 2 L4.100 Example 3 H9.100 Example 4 H7.100Example 5 H9.150 Example 6 H7.150 Example 7

Example 9

The performance of two high Tg samples, i.e. H9.100 and H9.150, werecompared to one another. All samples were direct coated to 2 mil mylarat 60 gsm+1-3, air dried for 5 min. followed by 10 min. in a 120° C.forced air oven. All samples were conditioned for 24 hours in acontrolled climate room. A summary of the samples and results ofperformance testing are set forth below in Tables 6A and 6B. Throughoutthese tables, “MOF” refers to mode of failure. “Zip” refers to quickzipping peels. “Sp” refers to cohesive splitting. “Re” refers toremoved. Regarding the samples, “% BOS” refers to percent based onsolids content. And “WPI” refers to Williams Plasticity Index.

TABLE 6A Test Results for Samples H9.100 and H9.150 180 DEG SS PEELSample XLINKER % BOS 15 MIN MOF AVG 24 HR AVG 72 HR AVG H9.100 4.71 5.866.68 5.06 4.88 5.99 5.94 6.91 6.76 4.86 5.97 6.7 H9.100 1:3:9 AAA 0.20%4.6 5.25 6.94 4.96 4.74 5.87 5.73 6.73 7.00 4.65 6.06 7.32 H9.100 1:3:9AAA 0.40% 3.78 5.95 6.42 3.45 zip 4.23 4.68 5.57 5.31 6.11 5.45 6.09 6.6H9.100 1:3:9 AAA 0.60% 4.6 5.47 6.23 4.64 4.39 5.04 5.39 5.76 6.18 3.93zip 5.65 6.54 H9.100 1:3:9 AAA 0.80% 3.42 zip 5.45 6.05 3.89 zip 3.735.32 5.39 5.93 6.09 3.89 zip 5.4 6.28 H9.150 1:3:9 AAA 0.20% 3.7 5.315.96 4.19 4.12 6.15 5.64 6.58 6.04 4.46 5.47 5.58 H9.150 1:3:9 AAA 0.40%3.77 5.47 5.92 3.97 3.66 5.46 5.25 5.54 5.65 3.24 4.81 5.48 H9.150 1:3:9AAA 0.60% 3.2 5.31 5.71 3.33 3.26 5 5.05 5.57 5.62 3.25 4.84 5.58 H9.1501:3:9 AAA 0.80% 3.24 4.93 4.8 3.02 3.38 5.1 4.94 5.32 5.04 3.89 4.8 4.99

TABLE 6B Test Results for Samples H9.100 and H9.150 8.8 LB PER SQ INSHEAR WPI Sample XLINKER % BOS MIN MOF AVG VALUE AVG H9.100 39.1 sp 28.5sp 33.27 NA 32.2 sp H9.100 1:3:9 AAA 0.20% 422.7 sp 1.9 473.7 sp 439.232.1 2 421.3 sp H9.100 1:3:9 AAA 0.40% 10000 re 3.3 10000 re 10000.003.31 3.305 10000 re H9.100 1:3:9 AAA 0.60% 10000 re 4.3 10000 re10000.00 4.3 4.3 10000 re H9.100 1:3:9 AAA 0.80% 10000 re 4.58 10000 re10000.00 4.59 4.585 10000 re H9.150 1:3:9 AAA 0.20% 10000 re 3.07 10000re 10000.00 3.15 3.11 10000 re H9.150 1:3:9 AAA 0.40% 10000 re 4.4110000 re 10000.00 4.85 4.63 10000 re H9.150 1:3:9 AAA 0.60% 10000 re5.27 10000 re 10000.00 5.97 5.62 10000 re H9.150 1:3:9 AAA 0.80% 10000re 5.48 10000 re 10000.00 5.99 5.735 10000 re

Example 10

The performance of two high Tg samples H7.100 and H7.150, were similarlycompared to one another. All samples were direct coated to 2 mil mylarat 60 gsm+/−3, air dried for 5 min. followed by 10 min. in a 120° C.forced air oven. All samples were conditioned for 24 hours by acontrolled climate room. A summary of the samples and results ofperformance testing are set forth below in Tables 7A and 7B.

TABLE 7A Test Results for Samples H7.100 and H7.150 180 DEG SS PEELSample XLINKER % BOS 15 MIN AVG 24 HR AVG 72 HR AVG H7.100 1:1:9 AAA0.50% 2.96 3.45 5.37 4.64 3.99 4.48 4.14 5.71 5.57 4.38 4.49 5.64 H7.1001:1:9 AAA 0.60% 4.12 4.19 5.38 3.11 3.61 4.08 4.15 5.24 5.34 3.59 4.195.41 H7.100 1:1:9 AAA 0.70% 3.26 4.48 5.39 3.67 3.41 3.85 4.15 4.82 5.253.29 4.12 5.53 H7.100 1:1:9 AAA 0.80% 3.29 3.77 4.85 3.36 3.44 3.66 3.704.99 4.99 3.67 3.66 5.17 H7.150 1:1:9 AAA 0.50% 4.74 4.31 3.85 4.53 4.423.83 4.44 3.97 4.54 4 5.18 5.8 H7.150 1:1:9 AAA 0.60% 3.85 4.39 5.123.98 4.04 4.95 4.79 5.58 5.48 4.3 5.02 5.73 H7.150 1:1:9 AAA 0.70% 4.254.66 5.32 3.84 4.12 4.43 4.58 5.08 5.15 4.26 4.64 5.06

TABLE 7B Test Results for Samples H7.100 and H7.150 8.8 LB PER SQ INSHEAR WPI Sample XLINKER % BOS MIN MOF AVG VALUE AVG H7.100 1:1:9 AAA0.50% 8300 re 4.16 8300 re 8300.00 4.01 4.085 8300 re H7.100 1:1:9 AAA0.60% 8300 re 4.4 8300 re 8300.00 4.11 4.255 8300 re H7.100 1:1:9 AAA0.70% 8300 re 5.1 8300 re 8300.00 4.8 4.95 8300 re H7.100 1:1:9 AAA0.80% 8300 re 5.01 8300 re 8300.00 5.03 5.02 8300 re H7.150 1:1:9 AAA0.50% 8300 re 4.11 8300 re 8300.00 5.2 4.655 8300 re H7.150 1:1:9 AAA0.60% 8300 re 4.25 8300 re 8300.00 5.57 4.91 8300 re H7.150 1:1:9 AAA0.70% 8300 re 5.71 8300 re 8300.00 5.5 5.605 8300 re

Example 11

The performance of two low Tg samples L4.100 and L6.100, were comparedto one another. All samples were direct coated to 2 mil mylar at 60gsm+1-3, air dried for 5 min. followed by 10 min. in a 120° C. forcedair oven. All samples were conditioned for 24 hours in a controlledclimate room. A summary of the samples and results of performancetesting are set forth below in Tables 8A and 8B.

TABLE 8A Test Results for Samples L.100 and L6.100 180 DEG SS PEELSAMPLE AAA % BOS 15 MIN MOF AVG 24 HR MOF AVG 72+ HR MOF AVG L4.1001:1:8 0.40% 3.84 sp 4.06 sp 4.14 sp AAA 4.01 sp 3.93 4.19 sp 4.11 4.21sp 4.14 3.95 sp 4.08 sp 4.08 sp L4.100 1:1:8 0.50% 4.52 sp 4.52 sp 4.60sp AAA 4.63 sp 4.55 4.53 sp 4.53 4.69 sp 4.64 4.50 sp 4.53 sp 4.64 spL4.100 1:1:8 0.60% 5.05 sp 5.17 sp 5.24 sp AAA 5.31 sp 5.27 5.35 sp 5.285.45 sp 5.40 5.44 sp 5.31 sp 5.50 sp L4.100 1:1:8 0.70% 5.44 sp 5.50 sp5.72 sp AAA 5.60 sp 5.56 5.55 sp 5.55 5.76 sp 5.74 5.63 sp 5.60 sp 5.74sp L4.100 1:1:8 0.80% 2.55 5.64 sp 6.11 sp AAA 2.40 2.64 5.87 sp 5.276.21 sp 6.21 2.96 4.30 6.30 sp L6.100 1:1:8 0.40% 7.38 sp 7.46 sp 7.83sp AAA 7.58 sp 7.65 7.58 sp 7.52 7.86 sp 7.82 7.98 sp 7.53 sp 7.76 spL6.100 1:1:8 0.50% 8.58 sp 8.04 sp 8.42 sp AAA 7.25 sp 8.04 8.36 sp 8.268.48 sp 8.47 8.28 sp 8.36 sp 8.51 sp L6.100 1:1:8 0.60% 7.83 p tr 8.35sp 8.44 sp AAA 6.10 p tr 5.96 6.12 lt tr 7.18 3.78 lt tr 6.95 3.94 p tr7.07 sp 8.62 sp L6.100 1:1:8 0.70% 3.40 7.03 p 9.07 sp AAA tr/sp 2.823.01 5.17 p tr 7.03 8.83 p sp 9.307 2.82 8.89 sp 9.30 sp L6.100 1:1:80.80% 3.10 4.91 6.11 AAA 3.08 2.98 4.87 4.91 5.14 6.11 2.77 4.95 7.07 ptr

In Table 8A and other tables, “p tr” refers to partial adhesivetransfer. And “It tr” refers to light partial adhesive transfer. And “ptr/sp refers to partial cohesive splitting.

TABLE 8B Test Results for Samples L.100 and L6.100 ½″ × ½″ × 1 kg SHEARSAMPLE AAA % BOS MIN MOF AVG L4.100 1:1:8 AAA 0.40% 1.6 sp 1.3 sp 1.45L4.100 1:1:8 AAA 0.50% 13.3 sp 11 sp 12.15 L4.100 1:1:8 AAA 0.60% 24.7sp 28.1 sp 26.40 L4.100 1:1:8 AAA 0.70% 50.4 sp 62.1 sp 56.25 L4.1001:1:8 AAA 0.80% 84.9 sp 89.4 sp 87.15 L6.100 1:1:8 AAA 0.40% 24.9 sp25.1 sp 25.00 L6.100 1:1:8 AAA 0.50% 87.2 sp 79 sp 83.10 L6.100 1:1:8AAA 0.60% 207.5 sp 162.5 sp 185.00 L6.100 1:1:8 AAA 0.70% 196.5 adh201.8 adh 199.15 L6.100 1:1:8 AAA 0.80% 105.4 adh 77.7 adh 91.55

In Table 8B and other tables, “adh” refers to adhesive failure.

Example 12

The performance of one of the high Tg samples H7.150 was evaluated in acoatweight study. All samples were direct coated to 2 mil. Mylar atdesignated coatweight, air dried for 5 min. followed by 120° C. for 10minutes. All samples were conditioned for 24 hours in a controlledclimate room. A summary of the samples and results of performancetesting are set forth below in Tables 9A and 9B.

TABLE 9A Test Results for Sample H7.150 AAA 180 DEG SS PEEL SAMPLE CW %BOS 15 MIN AVG 24 HR AVG 72 HR AVG H7.150 30 GSM 0.50% 2.42 4.34 5.272.64 2.59 5.48 4.94 6.34 5.53 2.72 5 4.97 H7.150 40 GSM 0.50% 3.59 5.315.23 3.33 3.24 5.21 5.06 5.42 5.09 2.79 4.66 4.61 H7.150 50 GSM 0.50%5.36 6.63 6.65 4.71 5.03 6.79 6.84 6.94 6.89 5.01 7.1 7.09

TABLE 9B Test Results for Sample H7.150 8.8 LB PER SQ 65 C. 1 × 1 × 5 LBAAA IN SHEAR SHEARS SAFT SAMPLE CW % BOS MIN AVG MIN SLIP/MOF AVG DEG C.MOF AVG H7.150 30 GSM 0.50% 10000 360 .2 mm 200 pass 10000 10000.00 360.1 mm 360 200 pass 200 10000 360 .1 mm 200 pass H7.150 40 GSM 0.50%10000 360 .2 mm 200 pass 10000 10000.00 360 .2 mm 360 200 pass 200 10000360 .2 mm 200 pass H7.150 50 GSM 0.50% 10000 360 .2 mm 200 pass 1000010000.00 360 .1 mm 360 200 pass 200 10000 360 .1 mm 200 pass

Example 13

The performance of two high Tg samples H9.100 and H7.100, was evaluatedin a coatweight study. All samples were direct coated to aluminum foilat designated coatweight, air dried for 5 min. followed by 120° C. for10 minutes. All samples were conditioned for 24 hours in a controlledclimate room. A summary of the samples and results of performancetesting are set forth below in Table 10.

TABLE 10 Test Results for Samples H9.100 and H7.100 1:3:9 AAA COAT 180DEG SS PEEL 8.8 LB PER SQ IN SHEAR SAMPLE % BOS WT 15 MIN AVG 24 HR AVG72 HR AVG MIN MOF AVG H9.100 0.60% 30 gsm 3 4.91 6.13 10000 re 2.57 3.085.53 5.32 4.55 5.40 10000 re 10000.00 3.67 5.52 5.51 10000 re 60 gsm5.22 7.29 6.85 1647.3 lt st 4.84 5.01 7.01 7.04 6.5 6.61 10000 re7215.77 4.97 6.82 6.49 10000 re 120 gsm  2.94 4.61 9.26 362.4 Lt st 4.33.83 5.93 5.28 8.28 8.25 10000 re 6787.47 4.26 5.3 7.21 10000 re H7.1000.70% 30 gsm 4.37 6.29 4.98 10000 re 3.98 3.85 5.42 5.93 5.22 5.28 10000re 10000.00 3.21 6.09 5.65 10000 re 60 gsm 3.1 4.85 5.37 10000 re 3.23.48 5.29 5.21 6.37 6.03 10000 re 10000.00 4.14 5.48 6.34 10000 re 120gsm  4.53 6.16 7.37 1993.3 Lt st 3.19 3.62 5.58 5.66 6.04 6.59 10000 re7331.10 3.15 5.24 6.36 10000 re

Example 14

Samples of a high Tg sample H9.150, were subjected to a drying study.All samples were direct coated to 2 mil mylar at 60+/−5 gsm, air driedfor 5 min. followed by the designated temperatures for 10 min. Allsamples were conditioned for 24 hours in a controlled climate room. Asummary is set forth below in Table 11.

TABLE 11 Test Results for Sample H9.150 8.8 LB PER SQ 180 DEG SS PEEL INSHEAR SAMPLE XLINKER % BOS 15 MIN AVG 24 HR AVG 72 HR AVG MIN AVG H9.1501:3:9 0.20% 3.76 5.03 5.6 10000 AAA dried 110 3.86 4.01 4.94 5.23 5.345.63 10000 10000.00 temp dry time  10 4.4 5.73 5.95 10000 H9.150 1:3:90.20% 4.77 5.62 5.95 10000 AAA dried 120 4.53 4.58 5.75 5.70 5.94 6.0110000 10000.00 temp dry time  10 4.43 5.73 6.14 10000 H9.150 1:3:9 0.20%3.85 5.5 5.77 10000 AAA dried 130 3.94 3.79 4.9 5.17 6.02 5.91 1000010000.00 temp dry time  10 3.59 5.11 5.94 10000 H9.150 1:3:9 0.20% 3.345.31 5.87 10000 AAA dried 140 3.25 3.33 5.04 5.20 5.95 5.90 1000010000.00 temp dry time  10 3.4 5.24 5.88 10000

Example 15

Samples of low Tg polymers, e.g., L4.100 and L6.100, were subjected toquick stick testing. All samples were direct coated to 2 mil mylar at 60gsm+1-3, air dried for 5 min. followed by 10 min. in a 120° C. forcedair oven. All samples were conditioned for 24 hours in a controlledclimate room. A summary of the samples and results of quick sticktesting are set forth below in Tables 12A and 12B.

TABLE 12A Test Results for Samples L4.100 and L6.100 180 DEG SS PEELSAM- 15 72+ PLE AAA % BOS MIN MOF AVG HR MOF AVG L4:100 1:1:8AAA 0.40%3.84 sp 4.14 sp 4.01 sp 3.93 4.21 sp 4.14 3.95 sp 4.08 sp L4.1001:1:8AAA 0.50% 4.52 sp 4.60 sp 4.63 sp 4.55 4.69 sp 4.64 4.50 sp 4.64 spL4.100 1:1:8AAA 0.60% 5.05 sp 5.24 sp 5.31 sp 5.27 5.45 sp 5.40 5.44 sp5.50 sp L4.100 1:1:8AAA 0.70% 5.44 sp 5.72 sp 5.60 sp 5.56 5.76 sp 5.745.63 sp 5.74 sp L4.100 1:1:8AAA 0.80% 2.55 6.11 sp 2.40 2.64 6.21 sp6.21 2.96 6.30 sp L6.100 1:1:8AAA 0.40% 7.38 sp 7.83 sp 7.58 sp 7.657.86 sp 7.82 7.98 sp 7.76 sp L6.100 1:1:8AAA 0.50% 8.58 sp 8.42 sp 7.25sp 8.04 8.48 sp 8.47 8.28 sp 8.51 sp L6.100 1:1:8AAA 0.60% 7.83 p tr8.44 sp 6.10 p tr 5.96 3.78 lt tr 6.95 3.94 p tr 8.62 sp L6.100 1:1:8AAA0.70% 3.40 9.07 sp 2.82 3.01 8.83 p sp 9.07 2.82 9.30 sp L6.100 1:1:8AAA0.80% 3.10 6.11 3.08 2.98 5.14 6.11 2.77 7.07 p tr

TABLE 12B Test Results for Samples L4.100 and L6.100 ½″ × ½″ × 1 kgSHEAR ROLLING BALL SS LOOPTACK SAMPLE AAA % BOS MIN MOF AVG VALUE (mm)AVG VALUE (mm) MOF AVG L4:100 1:1:8AAA 0.40% 1.6 sp 40 10.54 tr 1.3 sp1.45 50 45 9.84 tr 10.19 L4.100 1:1:8AAA 0.50% 13.3 sp 60 11.81 tr 11 sp12.15 48 54 11.68 tr 9.51 L4.100 1:1:8AAA 0.60% 24.7 sp 65 5.05 28.1 sp26.40 50 57.5 5.45 5.25 L4.100 1:1:8AAA 0.70% 50.4 sp 50 4.76 62.1 sp56.25 50 50 4.46 4.61 L4.100 1:1:8AAA 0.80% 84.9 sp 50 2.86 89.4 sp87.15 65 57.5 2.76 2.81 L6.100 1:1:8AAA 0.40% 24.9 sp 135 7.20 25.1 sp25.00 140 137.5 8.41 7.81 L6.100 1:1:8AAA 0.50% 87.2 sp 140 4.51 79 sp83.10 155 147.5 4.61 4.56 L6.100 1:1:8AAA 0.60% 207.5 sp 164 3.90 162.5sp 185.00 170 167 4.28 4.09 L6.100 1:1:8AAA 0.70% 196.5 adh 160 3.46201.8 adh 199.15 140 150 3.48 3.47 L6.100 1:1:8AAA 0.80% 105.4 adh 1403.40 77.7 adh 91.55 165 152.5 3.44 3.42

In Table 12B, the term “adh” means adhesive failure.

Example 16

Samples of low Tg polymer L4.100 and L6.100 were subjected toperformance testing. All samples were direct coated to 2 mil mylar at 60gsm+1-3, air dried for 5 min. followed by 10 min. in a 120° C. forcedair oven. All samples were conditioned for 24 hours in a controlledclimate room. A summary of the samples and results of testing are setforth below in Tables 13A and 13B.

TABLE 13A Test Results for Samples L4.100 and L6.100 180 DEG PP PEEL 72+SAMPLE AAA % BOS 15 MIN MOF AVG HR MOF AVG L4.100 1:1:8 0.40% 3.74 sp4.07 sp AAA 3.93 sp 3.85 4.24 sp 4.20 3.87 sp 4.28 sp L4.100 1:1:8 0.50%4.20 sp 4.54 sp AAA 4.46 sp 4.39 4.77 sp 4.70 4.50 sp 4.80 sp L4.1001:1:8 0.60% 0.82 zip 5.46 sp AAA 0.81 zip 0.80 0.72 zip 2.33 0.78 zip0.82 zip L4.100 1:1:8 0.70% 0.77 zip 0.64 zip AAA 0.74 zip 0.76 0.71 zip0.70 0.76 zip 0.74 zip L4.100 1:1:8 0.80% 2.16 2.57 AAA 2.46 2.37 2.862.72 2.50 2.72 L6.100 1:1:8 0.40% 0.48 zip 0.39 zip AAA 0.41 zip 0.460.60 zip 0.45 0.49 zip 0.37 zip L6.100 1:1:8 0.50% 0.45 zip 0.34 zip AAA0.47 zip 0.46 0.40 zip 0.36 0.47 zip 0.34 zip L6.100 1:1:8 0.60% 0.41zip 0.39 zip AAA 0.40 zip 0.39 1.00 zip 0.58 0.36 zip 0.35 zip L6.1001:1:8 0.70% 1.46 sl zip 2.54 AAA 1.14 sl zip 1.478 2.33 2.56 1.84 sl zip2.77 L6.100 1:1:8 0.80% 1.94 2.22 AAA 1.68 1.89 2.17 2.29 2.04 2.47

TABLE 13B Test Results for Samples L4.100 and L6.100 180 DEG HDPE PEEL15 SAMPLE AAA % BOS MIN MOF AVG 72+ HR MOF AVG L4.100 1:1:8 0.40% 3.99sp 4.30 sp AAA 3.96 sp 4.02 4.15 sp 4.25 4.12 sp 4.31 sp L4.100 1:1:80.50% 3.01 p tr 4.65 sp AAA 2.76 p tr 2.42 4.54 sp 4.65 1.50 p tr 4.75sp L4.100 1:1:8 0.60% 0.61 0.73 AAA 0.69 0.65 0.80 0.73 0.64 0.65 L4.1001:1:8 0.70% 0.44 0.51 AAA 0.38 0.42 0.67 0.59 0.45 0.58 L4.100 1:1:80.80% 0.31 0.36 AAA 0.25 0.28 0.43 0.39 0.29 0.38 L6.100 1:1:8 0.40%0.84 1.21 AAA 0.87 0.90 0.95 1.03 1.00 0.93 L6.100 1:1:8 0.50% 0.66 0.65AAA 0.60 0.62 0.83 0.71 0.60 0.64 L6.100 1:1:8 0.60% 0.50 0.64 AAA 0.430.48 0.64 0.61 0.52 0.55 L6.100 1:1:8 0.70% 0.40 0.48 AAA 0.44 0.40 0.410.46 0.37 0.48 L6.100 1:1:8 0.80% 0.36 0.33 AAA 0.35 0.34 0.36 0.34 0.300.34

Example 17

Samples of high Tg polymers H9.150 and H7.150, were subjected to ULtesting. All samples were direct coated to foil at 60+/−5 gsm, air driedfor 5 min. followed by 120° C. for the designated minutes. All sampleswere conditioned for 24 hours in a controlled climate room. A summary ofthe samples and results of testing are set forth below in Tables 14A and14B.

TABLE 14A Test Results for Samples H9.150 and H7.150 180 DEG SS PEELSAM- 15 24 72 PLE XLINKER % BOS MIN AVG HR AVG HR AVG H9.150 1:1:8AAA0.40% 6.4 7.66 8.08 5.54 5.29 6.62 6.80 6.56 6.52 3.92 6.13 4.91 H9.1501:1:8AAA 0.50% 6.06 7.41 8.3 5.78 6.07 7.34 7.44 8.27 8.24 6.37 7.578.16 H9.150 1:1:8AAA 0.60% 5.62 7.58 7.99 5.36 4.98 6.81 6.37 7.11 7.553.82 4.73 7.54 H7.150 1:1:8AAA 0.50% 5.95 6.8 7.63 5.29 5.62 6.42 6.637.07 7.45 5.61 6.67 7.65 H7.150 1:1:8AAA 0.60% 4.98 5.7 6.56 5.19 5.005.81 5.69 5.98 6.25 4.82 5.57 6.21 H7.150 1:1:8AAA 0.70% 3.73 3.56 3.534.96 4.22 4.54 4.21 5.6 4.75 3.98 4.52 5.11

TABLE 14B Test Results for Samples H9.150 and H7.150 65 C. 1 × 1 × 5 lb8.8 LB PER SQ IN 1 × 1 × 10 lb SLIP/ SHEAR SAMPLE XLINKER % BOS MINSLIP/MOF AVG MIN MOF AVG MIN MOF AVG H9.150 1:1:8AAA 0.40% 7200 .5 mm163.10 Sp 1000 re 7200 .6 mm 7200.00 181.80 Sp 175.53 1000 re 10000.007200 .6 mm 181.70 sp 1000 re H9.150 1:1:8AAA 0.50% 7200 .4 mm 360.00 .9mm 1000 re 7200 .4 mm 7200.00 360.00 .9 mm 360.00 1000 re 10000.00 7200.4 mm 360.00 .9 mm 1000 re H9.150 1:1:8AAA 0.60% 7200 .3 mm 360.00 .5 mm1000 re 7200 .2 mm 7200.00 360.00 .4 mm 360.00 1000 re 10000.00 7200 .2mm 360.00 .5 mm 1000 re H7.150 1:1:8AAA 0.50% 7200 .3 mm 360.00 .5 mm1000 re 7200 .3 mm 7200.00 360.00 .5 mm 360.00 1000 re 10000.00 7200 .3mm 360.00 .5 mm 1000 re H7.150 1:1:8AAA 0.60% 7200 .1 mm 360.00 .2 mm1000 re 7200 .2 mm 7200.00 360.00 .2 mm 360.00 1000 re 10000.00 7200 .1mm 360.00 .1 mm 1000 re H7.150 1:1:8AAA 0.70% 7200 .2 mm 360.00 .2 mm1000 re 7200 .2 mm 7200.00 360.00 .2 mm 360.00 1000 re 10000.00 7200 .2mm 360.00 .3 mm 1000 re

Example 18

Samples of high Tg polymers, i.e., H7.100 and H9.100, were subjected toUL testing. All samples were directed coated to foil at 60+/−5 gsm, airdried for 5 min. followed by 120° C. for the designated minutes. Allsamples were conditioned for 24 hours in a controlled climate room. Asummary of the samples and results of testing are set forth below inTables 15A and 15B.

TABLE 15A Test Results for Samples H7.100 and H9.100 180 DEG SS PEELSAM- X- 15 24 72 PLE LINKER % BOS MIN AVG HR AVG HR AVG H7.100 1:1:9AAA0.60% 5.31 6 6.02 5.51 5.00 5.83 5.56 7.01 6.29 4.19 4.85 5.83 H7.1001:1:9AAA 0.70% 5.04 5.2 6.21 3.62 4.34 5.77 5.35 6.67 6.43 4.36 5.096.41 H7.100 1:1:9AAA 0.80% 4.34 4.6 5.13 4.57 4.19 5.78 5.00 6.2 5.483.65 4.63 5.11 H9.100 1:1:9AAA 0.50% 6.19 6.84 6.71 5.12 5.77 6.43 6.966.96 7.09 6.01 7.6 7.61 H9.100 1:1:9AAA 0.60% 6.2 6.41 5.89 5.59 5.676.46 6.27 7.25 6.44 5.23 5.95 6.19 H9.100 1:1:9AAA 0.70% 5.63 6.97 7.156.06 6.00 7.01 7.08 7.16 7.30 6.32 7.27 7.58

TABLE 15B Test Results for Samples H7.100 and H9.100 1 × 1 × 5 lb 65 1 ×1 × 10 lb DEG Shears 8.8 LB PER SQ IN SHEAR SAMPLE X-LINKER % BOS MINMOF AVG MIN MOF AVG MIN MOF AVG H7.100 1:1:9AAA 0.60% 6000+ N/A 360.00.1 mm 1000 re 6000+ 6000.00 360.00 .1 mm 360.00 1000 re 10000.00 6000+360.00 .1 mm 1000 re H7.100 1:1:9AAA 0.70% 6000+ 360.00 .1 mm 4134.7ltst 6000+ 6000.00 360.00 .1 mm 360.00 1000 re 8044.90 6000+ 360.00 .2mm 1000 re H7.100 1:1:9AAA 0.80% 6000+ 360.00 .1 mm 1273.1 ltst 6000+6000.00 360.00 .1 mm 360.00 418.9 ltst 3897.33 6000+ 10000 re H9.1001:1:9AAA 0.50% 7200.00 .3 mm 360.00 .5 mm 10000 re 7200.00 .4 mm 7200.00360.00 .5 mm 360.00 10000 re 10000.00 7200.00 .3 mm 360.00 .5 mm 10000re H9.100 1:1:9AAA 0.60% 7200.00 .3 mm 360.00 .3 mm 10000 re 7200.00 .2mm 7200.00 360.00 .2 mm 360.00 10000 re 10000.00 7200.00 .2 mm 360.00 .2mm 10000 re H9.100 1:1:9AAA 0.70% 7200.00 .1 mm 360.00 .2 mm 10000 re7200.00 .2 mm 7200.00 360.00 .2 mm 360.00 10000 re 10000.00 7200.00 .1mm 360.00 .2 mm 10000 re

In Tables 15B and other tables, the term “lt st” refers to light stain.

Example 19

Samples of low Tg polymers L4.100 and L6.100 were subjected to variousbenchmarking trials. All experimental samples were direct coated to 2mil mylar at 60+/−5 gsm, air dried for 5 min. followed by 120° C. forthe designated minutes. All samples were conditioned for 24 hours in acontrolled climate room. A summary of the samples and results of thetrials are set forth below in Tables 16A and 16B.

TABLE 16A Test Results for Samples L4.100 and L6.100 AAA Polymer Level15 MIN MOF AGED MOF AGED MOF AGED MOF AGED MOF L4.100  0.0% 5.56 sp 5.76sp 0.59 0.7 zip 1.05 L4.100 0.80% 2.64 6.21 sp 0.39 2.72 0.42 L6.1000.60% 5.96 ptr 6.95 sp 0.61 0.58 zip 0.9 L6.100 0.70% 3.01 9.07 sp 0.452.56 0.52

TABLE 16B Test Results for Samples L4.100 and L6.100 ROLLING 8.8 LB AAASS LOOP-TACK BALL PER SQ IN POLYMER Level 15 MIN VALUE (mm) MIN L4.1000.70% 4.61 50.0 56.25 L4.100 0.80% 2.81 57.5 87.15 L6.100 0.60% 4.09167.0 185.00 L6.100 0.70% 3.47 150.0 199.15

Example 20

Samples of high Tg polymers H9.150 and H7.150 were subjected to variousbenchmarking trials. All samples were directed coated to foil at 60+/−5gsm, air dried for 5 min. followed by 120° C. for the designatedminutes. All samples were conditioned for 24 hours in a controlledclimate room. A summary of the samples and results of benchmarking areset forth below in Tables 17A and 17B.

TABLE 17A Comparative Test Results for Samples H9.150 and H7.150 180 DEGSS PEEL 1 × 1 × 10 lb SAMPLE XLINKER % BOS 15 MIN AVG 24 HR AVG 72 HRAVG MIN SLIP/MOF AVG H9.150 1:1:8AAA 0.60% 4.51 6.54 7.23 10000 .2 mm4.3 4.34 6.33 6.20 7.17 6.42 10000 .2 mm 10000.00 4.22 5.72 4.85 10000.1 mm H7.150 1:1:8AAA 0.60% 3.97 5.71 6.27 10000 .2 mm 3.36 3.51 5.275.31 6 5.83 10000 .2 mm 10000.00 3.2 4.96 5.21 10000 .2 mm Venture tape1581A 3.37 5.05 5.46 196.00 ltst 3.45 3.53 5.17 5.19 5.59 5.60 268.10ltst 242.33 3.77 5.36 5.74 262.90 ltst Shurtape AF 912 6.3 7.13 7.61126.30 ltsp 5.35 5.62 6.44 6.61 6.79 7.03 125.50 ltsp 126.03 5.22 6.256.68 126.30 ltsp Shurtape AF 100 3.66 4.81 5.14 4148.50 sp 3.74 3.715.07 5.02 5.64 5.31 2462.00 sp 4603.50 3.73 5.17 5.14 7200.00 .1 mmFasson 181 AP 3.66 3.67 5.41 655.10 ltst 3.63 4.20 4.3 4.60 4.59 5.211641 ltst 1376.80 5.32 5.83 5.62 1834.3 ltst Shurtape DC 181 2.02 3.214.22 53.5 ltsp 1.57 1.71 3.43 3.31 3.72 4.82 62.5 ltsp 71.67 1.54 3.296.52 99 ltsp Polyken 339 3.66 5.19 5.67 N/A 3.80 3.70 4.59 4.83 4.074.95 N/A 3.65 4.72 5.11

TABLE 17B Comparative Test Results for Samples H9.150 and H7.150 1 × 1 ×5 lb 8.8 LB PER SQ IN SHEAR SAMPLE X-LINKER % BOS MIN SLIP/MOF AVG MINMOF AVG H9.150 1:1:8AAA 0.60% 360.00 .3 mm 10000 re 360.00 .2 mm 360.0010000 re 10000.00 360.00 .3 mm 10000 re H7.150 1:1:8AAA 0.60% 360.00 .5mm 10000 re 360.00 .4 mm 360.00 10000 re 10000.00 360.00 .5 mm 10000 reVenture tape 1581A 71.20 pop 49 ltst 33.90 pop 39.40 41.5 ltst 45.2513.10 pop Shurtape AF 912 24.00 ltsp 5287.1 ltsp 14.80 ltsp 17.57 10000re 7643.55 13.90 .ltsp Shurtape AF 100 360.00 .2 mm 215.7 pop 360.00 .1mm 360.00 193.3 pop 204.50 360.00 .2 mm Fasson 181 AP 360 .2 mm 808.6ltst 360 .2 mm 360.00 10000 re 5404.30 360 .2 mm Shurtape DC 181 118.5sp 727 ltsp 91.4 sp 106.63 49.7 ltsp 61.20 110.00 sp Polyken 339 31.8pop 81 pop 52.30 pop 32.40 43.4 pop 62.20 13.10 pop

In Table 17B and other tables, the term “pop” refers to quick adhesivefailure.

Example 21

Samples of high Tg polymers H9.100 and H7.100, were subjected toadditional benchmarking trials. All samples were direct coated to foilat 60+/−5 gsm, air dried for 5 min followed by 120° C. for thedesignated minutes. All samples were conditioned for 24 hours in acontrolled climate room. A summary of the samples and results ofbenchmarking are set forth below in Tables 18A and 18B

TABLE 18A Comparative Test Results for Samples H9.100 and H7.100 180 DEGSS PEEL 1 × 1 × 10 lb SAMPLE X-LINKER % BOS 15 MIN AVG 24 HR AVG 72 HRAVG MIN SLIP/MOF AVG H9.100 1:1:8AAA 0.70% 5.63 6.97 7.15 7200    .1 mm6.06 6.00 7.01 7.08 7.16 7.30 7200    .2 mm 7200.00 6.32 7.27 7.587200    .1 mm H7.100 1:1:8AAA 0.80% 4.34 4.6 5.13 6000+   n/a 4.57 4.195.78 5.00 6.2 5.48 6000+   n/a n/a 3.65 4.63 5.11 6000+   n/a Venturetape 1581A 3.37 5.05 5.46 196.00 ltst 3.45 3.53 5.17 5.19 5.59 5.60268.10 ltst 242.33 3.77 5.36 5.74 262.90 ltst Shurtape AF 912 6.3 7.137.61 126.30 ltsp 5.35 5.62 6.44 6.61 6.79 7.03 125.50 ltsp 126.03 5.226.25 6.68 126.30 ltsp Shurtape AF 100 3.66 4.81 5.14 4148.50  sp 3.743.71 5.07 5.02 5.64 5.31 2462.00  sp 4603.50 3.73 5.17 5.14 7200.00  .1mm Fasson 181 AP 3.66 3.67 5.41 655.10 ltst 3.63 4.20 4.3 4.60 4.59 5.211641    ltst 1376.80 5.32 5.83 5.62 1834.3  ltst Shurtape DC 181 2.023.21 4.22 53.5 ltsp 1.57 1.71 3.43 3.31 3.72 4.82 62.5 ltsp 71.67 1.543.29 6.52 99   ltsp Polyken 339 3.66 5.19 5.67 N/A 3.80 3.70 4.59 4.834.07 4.95 n/a 3.65 4.72 5.11

TABLE 18B Comparative Test Results for Samples H9.100 and H7.100 8.8 LBPER SQ 1 × 1 × 5 lb IN SHEAR SAMPLE X-LINKER % BOS MIN SLIP/MOF AVG MINMOF AVG H9.100 1:1:8AAA 0.70% 360.00 .2 mm 10000 re 360.00 .2 mm 360.0010000 re 7200.00 360.00 .2 mm 10000 re H7.100 1:1:8AAA 0.80% 360.00 .1mm 1273.1 ltst 360.00 .1 mm 360.00 418.9 ltst 3897.33 360.00 .1 mm 10000re Venture tape 1581A 71.20 pop 49 ltst 33.90 pop 39.40 41.5 ltst 45.2513.10 pop Shurtape AF 912 24.00 ltsp 5287.1 ltsp 14.80 ltsp 17.57 10000re 7643.55 13.90 .ltsp Shurtape AF 100 360.00 .2 mm 215.7 pop 360.00 .1mm 360.00 193.3 pop 204.50 360.00 .2 mm Fasson 181 AP 360 .2 mm 808.6ltst 360 .2 mm 360.00 10000 re 5404.30 360 .2 mm Shurtape DC 181 118.5sp 727 ltsp 91.4 sp 106.63 49.7 ltsp 61.20 110.00 sp Polyken 339 31.8pop 81 pop 52.30 pop 32.40 43.4 pop 62.20 13.10 pop

Example 22

Samples of High Tg polymer, i.e., H9.150, were subjected to acceleratedheat aging. Specifically, the samples were subjected to one (1) weekexposure to 65° C. All samples were direct coated to 2 mil mylar at60+/−5 gsm, air dried for 5 min. followed by 120° C. for the designatedminutes. All samples were conditioned for 24 hours in a controlledclimate room. A summary of the samples and results of testing are setbelow in Table 19.

TABLE 19 Comparative Test Results for Samples H9.150 and H7.150 180 DEGSS PEEL 8.8 LB PER SQ IN SHEAR SAMPLE XLINKER % BOS 15 MIN AVG 24 HR AVG72 HR AVG MIN MOF AVG H9.150 1:3:9 0.40% 4.52 5.08 6.11 10000 AAA AGED4.37 4.52 5 5.05 5.97 6.03 10000 10000.00 4.67 5.06 6.01 10000 H9.1501:3:9 0.40% 3.77 5.47 5.92 10000 AAA CONTROL 3.97 3.66 5.46 5.25 5.545.65 10000 10000.00 3.24 4.81 5.48 10000

The “control” in Table 19 is H9.150 not heat aged.

Example 23

Additional samples of high Tg polymer, i.e., H9.150, were subjected toaccelerated heat aging. All samples were direct coated to 2 mil mylar at60+/−5 gsm, air dried for 5 min. followed by 120° C. for the designatedminutes. All samples were conditioned accordingly. A summary of thesamples and results of testing are set forth below in Table 20.

TABLE 20 Test Results for Sample H9.150 8.8 LB PER SQ IN AAA 180 DEG SSPEEL SHEAR SAMPLE DWELL % BOS 15 MIN AVG 24 HR AVG 72 HR AVG MIN AVGH9.150 24 HR 0.20% 5.16 6.1 6.24 10000 CONTROL 4.56 4.90 5.78 6.00 6.126.25 10000 10000.00 4.98 6.12 6.4 10000 H9.150 Tappi room 0.20% 4.686.58 6.62 10000 dwell 3.97 4.33 5.39 5.91 6.34 6.16 10000 10000.00 4.355.77 5.52 10000 H9.150 60° oven dwell 0.20% 5.1 5.13 7.08 10000 4.454.89 5.8 5.55 6.31 6.27 10000 10000.00 5.12 5.73 5.42 10000

Many other benefits will not doubt become apparent from futureapplication and development of this technology.

All patents, applications, and articles noted herein are herebyincorporated by reference in their entirety.

As described hereinabove, the present subject matter solves manyproblems associated with previously known compositions and methods.However, it will be appreciated that various changes in the details,materials and arrangements of components and/or operations, which havebeen herein described and illustrated in order to explain the nature ofthe subject matter, may be made by those skilled in the art withoutdeparting from the principle and scope of the subject matter asexpressed in the appended claims.

What is claimed is:
 1. An acrylic polymer comprising: a first reactivesegment that includes at least one monomer having a self reactivefunctional group; and a second reactive segment that includes at leastone monomer having a reactive functional group.
 2. The acrylic polymerof claim 1 wherein the reactive functional group of the second reactivesegment is a self reactive functional group.
 3. The acrylic polymer ofclaim 2 wherein the self reactive functional group of the secondreactive segment is the same as the self reactive functional group ofthe first reactive segment.
 4. The acrylic polymer of claim 2 whereinthe self reactive functional group of the second reactive segment isdifferent than the self reactive functional group of the first reactivesegment.
 5. The acrylic polymer of claim 1 wherein the self reactivefunctional group is selected from the group consisting of silyl,anhydrides, epoxies, alkoxymethylol, and cyclic ethers.
 6. The acrylicpolymer of claim 5 wherein the self reactive functional group is anepoxy.
 7. The acrylic polymer of claim 1 wherein the reactive functionalgroup is selected from the group consisting of acids, hydroxyls, amines,and thiols.
 8. The acrylic polymer of claim 7 wherein the reactivefunctional group is an acid.
 9. The acrylic polymer of claim 1 whereinthe polymer has a polydispersity of less than 4.0.
 10. The acrylicpolymer of claim 9 wherein the polymer has a polydispersity of less than3.5.
 11. The acrylic polymer of claim 9 wherein the polymer has apolydispersity of less than 3.0.
 12. The acrylic polymer of claim 9wherein the polymer has a polydispersity of less than 2.5.
 13. Theacrylic polymer of claim 9 wherein the polymer has a polydispersity ofless than 2.0.
 14. The acrylic polymer of claim 1 wherein the polymerhas a number average molecular weight (Mn) within the range of fromabout 40,000 to about 150,000.
 15. The acrylic polymer of claim 14wherein the polymer has a number average molecular weight (Mn) withinthe range of from about 50,000 to about 110,000.
 16. The acrylic polymerof claim 1 wherein the first reactive segment and the second reactivesegment are molecularly miscible before cure as expressed by theirproperties in the bulk state that are indicative of a single phasebehavior.
 17. A pressure sensitive adhesive composition comprising: anacrylic polymer according to claim 1; and a crosslinking agent.
 18. Theadhesive composition of claim 17 further comprising: at least one agentselected from the group consisting of pigments, fillers, plasticizers,diluents, antioxidants, tackifiers, polymeric additives, andcombinations thereof.
 19. A method of preparing a pressure sensitiveadhesive composition comprising: polymerizing at least one monomerhaving a self reactive functional group to thereby form a first reactivesegment; polymerizing at least one monomer having a reactive functionalgroup to thereby form a second reactive segment; wherein at least one ofthe first reactive segment and the second reactive segment includes anacrylate group; forming an acrylic polymer from the first reactivesegment and the second reactive segment.
 20. The method of claim 19wherein at least one of the first reactive segment and the secondreactive segment is polymerized in the presence of a RAFT agent.
 21. Themethod of claim 19 wherein at least one of the first reactive segmentand the second reactive segment is polymerized in the presence of anSFRP agent.
 22. The method of claim 19 further comprising the step ofcrosslinking the functional groups of the reactive segments.